Dinuclear Alkynyl Gold(I) Complexes Containing Bridging N ...

Article 

pubs.acs.org/Organometallics 

Dinuclear Alkynyl Gold(I) Complexes Containing Bridging 

N‐Heterocyclic Dicarbene Ligands: New Synthetic Routes and 

Luminescence 

Juan Gil-Rubio,* ,† Verońica Caḿara, † Delia Bautista, ‡ and JoséVicente* ,† 

† Grupo de Química Organometaĺica, Departamento de Química Inorgańica, Facultad de Química, Universidad de Murcia, E-30071 

Murcia, Spain 

‡ SAI, Universidad de Murcia, E-30071 Murcia, Spain 

*S Supporting Information 

ABSTRACT: A series of dinuclear alkynyl gold(I) complexes 

of the type [(AuCCR′) 2 {μ-(Im-R) 2 (CH 2 ) n }] (R′ = t Bu, 

SiMe 3 , Ph, C 6 H 4 X-4 (X = OMe, CF 3 ,orNO 2 ), 3-pyridyl (Pyl), 

2,2′-bipyridin-5-yl (Bpyl); Im-R = N-methylimidazol-N-yl-2- 

ylidene (Im-Me), N-butylimidazol-N-yl-2-ylidene (Im-Bu), N- 

benzylimidazol-N-yl-2-ylidene (Im-Bz); n = 1, 3, 5) have been 

synthesized by (1) deprotonation of arylacetylenes with 

K 2 CO 3 in the presence of [(AuCl) 2 {μ-(Im-R) 2 (CH 2 ) n }], (2) 

the “acac method”, i.e., the reaction of [(AuCl) 2 {μ-(Im- 

R) 2 (CH 2 ) n }] with Tl(acac) and, subsequently, with HCCR′, and (3) the reaction of [Au(CCR′)] n with [(AgBr) 2 {μ-(Im- 

R) 2 (CH 2 ) n }]. In addition, mononuclear complexes [(AuCCR′)(Im-R 2 )], where Im-R 2 = N,N′-dimethylimidazol-2-ylidene and 

R′ = SiMe 3 or Im-R 2 = N,N′-dibenzylimidazol-2-ylidene and R′ = t Bu, have been prepared by method 2 or 3, respectively. A 

dinuclear complex containing two AuCl units connected by an acyclic dicarbene ligand results from the attack of N,N′- 

diethylpropylenediamine to the isocyanide ligand of [AuCl(CN t Bu)]. The photophysical properties of the new gold(I) chloro 

and alkynyl bis(carbene) complexes have been studied. Most of the dinuclear alkynyl complexes prepared are emissive at room 

temperature in the solid state or in solution. Complexes derived from aryl- or heteroarylalkynes give structured emissions that 

have been assigned to gold-perturbed intraligand 3 [π→π*](CCAr) excited states. 

■ INTRODUCTION 

Alkynyl gold(I) complexes have been extensively studied 

because they combine singular structural and photophysical 

features. 1 Their most remarkable structural features are related 

to their rod-like geometry and their marked tendency to form 

aggregates by intra- or intermolecular aurophilic interactions, 2 

which make them interesting building blocks for the synthesis 

of organometallic rod-shaped oligomers and polymers, 3−6 

liquid crystals, 7,8 macrocycles, 4,9,10 catenanes, 4 helicates, 11 and 

dendrimers. 12 Their photophysical behavior is characterized by 

a strong spin−orbit coupling, leading to emissive triplet states, 

the energy and luminescence efficiency of which can be deeply 

affected by the aurophilic interactions. 13 These properties have 

been exploited to prepare ion probes, 14,15 molecular switches, 16 

and electroluminescent devices. 17,18 

In contrast with the extensively studied alkynyl gold(I) 

complexes with auxiliary phosphine ligands, 1 alkynyl(carbene) 

gold(I) derivatives have received only little attention. 3,19−30 

The first such compounds were obtained by reacting alkynyl 

isocyanide complexes with amines (Scheme 1), which afforded 

acyclic diaminocarbene complexes. 22 This method was 

successfully applied to di- and trialkynyl derivatives. 3,19,20,22 

Gold(I) alkynyls containing N-heterocyclic carbene (NHC) 

ligands have been obtained (Scheme 1) (a) by reacting a 

Scheme 1 

NHC(chloro) gold(I) complex with a terminal alkyne in the 

presence of base, 23,25,28,29 (b) by transmetalation using 

MgCl(CCH) 24 or [Ag(CCPh)] n , 23 (c) by reacting a 

Received: May 18, 2012 

Published: August 1, 2012 

© 2012 American Chemical Society 5414 dx.doi.org/10.1021/om300431r | Organometallics 2012, 31, 5414−5426

Organometallics 

hydroxo(carbene) gold(I) complex with a terminal alkyne or 

with a 1-trimethylsilylalkyne, 26,27 or (d) by replacement of PR 3 

by a NHC ligand in [Au(CCR)(PR 3 )]. 18 Some of them are 

photoluminescent, and their emissions have been attributed to 

metal-perturbed alkynyl-based states. 23,25,26,28 In addition, 

several patents have reported the application of mononuclear 

alkynyl(carbene) gold(I) complexes as emitters in electroluminescent 

devices. 18 

Complexes containing two or more alkynyl gold(I) units 

connected by a multidentate phosphine or isocyanide ligand 

have been studied because of their aurophilic interactions and 

luminescence. 10,14,31−33 In recent years, bidentate NHC ligands 

with variable geometry, steric bulk, and donor ability have 

become available. 34,35 Herein we report the first series of 

dinuclear gold(I) alkynyls containing bridging dicarbene 

ligands. In addition, we have developed two new synthetic 

routes for this type of compound: (a) the reaction of 

acetylacetonato(carbene) gold(I) complexes with terminal 

alkynes (“acac” method), 36 and (b) the carbene-transfer 

reaction from a silver carbene complex to an acetylide gold(I) 

derivative. Finally, the photophysical properties of the new 

alkynyl complexes have been studied and compared to those of 

related 

■ 

alkynyl(phosphino) gold(I) compounds. 

RESULTS AND DISCUSSION 

Synthesis and Structural Characterization. Silver 

carbene precursors L n RAg 2 Br 2 (Scheme 2) were obtained in 

bond cleavage. Unfortunately, no good-quality single crystals of 

the new silver complexes were obtained; in addition, as they are 

soluble only in d 6 -DMSO, no low-temperature NMR studies 

could be conducted. 

Complexes L n RAg 2 Br 2 are effective carbene-transfer agents, 35 

reacting with [AuCl(SMe 2 )] at room temperature to give good 

yields of complexes L n RAu 2 Cl 2 (Scheme 2). The NMR spectra 

of the gold(I) complexes obtained agree with their symmetrical 

structures, and the C−Au carbon nucleus is more shielded than 

in L n RAg 2 Br 2 , giving a narrow singlet in the range 169.7−172.7 

ppm. 

Dinuclear alkynyl gold(I) complexes L n R(AuCCR′) 2 were 

prepared using three different methods (Scheme 3): 

Scheme 3 

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Scheme 2 

high yield by reacting the corresponding diimidazolium 

bromides (L n RH 2 )Br 2 (R = benzyl (Bz), n =1 37 or 3; 38 R= 

n Bu, n =1 39 or 3; 40 R = Me, n =3 41 or 5 42 ) with Ag 2 Oin 

acetonitrile. The synthesis and X-ray crystal structures of 

complexes L 1 BzAg 2 Br 2 43 and L 5 MeAg 2 Br 2 42 have been already 

reported, showing that the former is a tetranuclear species, 

[Ag 4 (μ-Br) 4 (μ-L 1 Bz) 2 ], while the second can be described as 

[Ag 2 (μ-L 5 Me) 2 ][AgBr 2 ] 2 . The NMR spectra of complexes 

L n RAg 2 Br 2 show the resonances expected for the symmetrical 

dicarbene ligands. A broad singlet in their 13 C{ 1 H} NMR 

spectrum (179.1−180.9 ppm, RT), corresponding to the C−Ag 

carbon nuclei, suggests a fast exchange process involving Ag−C 

Method A: By reacting chloro complexes L n RAu 2 Cl 2 with 

Tl(acac) (acac = acetylacetonato) and, subsequently, with 

HCCR′ (R′ = alkyl, aryl, or trimethylsilyl). In this application 

of the “acac” method, 36 we could not isolate the intermediate 

acetylacetonato complexes owing to their low stability. It 

should be noted that this method allows the synthesis of 

gold(I) trimethylsilylethynyl carbene complexes avoiding basepromoted 

desilylation. 

Method B: The reaction of [Au(CCR)] n with silver 

complexes L n RAg 2 Br 2 . This new method of synthesis of carbene 

gold(I) acetylides makes use of two well-known facts: (i) 

[Au(CCR)] n polymers react with neutral or anionic ligands, 

such as phosphines, 3,14,19,20,32,44− 47 isocyanides, 

3,8,15,16,19,20,45−48 or Cl − , 49 to give complexes of the 

type [Au(CCR)L] or [Au(CCR)Cl] − , respectively, and 

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dx.doi.org/10.1021/om300431r | Organometallics 2012, 31, 5414−5426


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(ii) silver carbene complexes are good carbene-transfer 

agents. 35,50 We note that, even though AgBr precipitation 

occurs during the reaction, the crude gold alkynyls still 

contained some soluble silver impurity, which was removed 

by stirring their solutions with excess Na 2 S 2 O 3·5H 2 O. 

Method C: The reaction of a chloro complex L n RAu 2 Cl 2 with 

HCCR′ in the presence of K 2 CO 3 . This method failed for 

the reactions of L 3 RAu 2 Cl 2 (R = n Bu or Me) with HCCPh, 

affording impure L 3 R(AuCCPh) 2 , and for the reaction of 

L 5 MeAu 2 Cl 2 with HCC t Bu, which gave a mixture where the 

expected alkynyl L 5 Me(AuCC t Bu) 2 was a minor component. 

Complexes L R AuCCR′ (Chart 1) were prepared from 

L Me AuCl 51 and HCCSiMe 3 using method A or from 

[Au(CC t Bu)] n and L Bz AgBr 52 using method B. 

Chart 1 

The NMR spectra of the gold alkynyl carbene complexes 

gave the expected signals according to the high symmetry of the 

molecules. The C−Au carbene carbon nuclei are deshielded by 

ca. 16 ppm with respect to their parent chloro complexes 

L n RAu 2 Cl 2 , which could be attributed to the stronger trans 

influence of the alkynyl ligand and the greater electronegativity 

of the chloro ligand. The chemical shifts of the acetylenic 

carbons were not significantly affected by the nature of the 

substituents of the carbene ligands, but depended on the alkyne 

substituents as previously noted. 22 In the IR spectra of all 

complexes, the ν(CC) bands appeared in the range 2020− 

2116 cm −1 . The crystal structure of L 3 Bu(AuCCPh) 2 has 

been determined (Figure 1). 

Acyclic diamino carbene (ADC) gold(I) complexes have 

been obtained by reacting amines with isocyanide gold(I) 

complexes. 21,45 We have attempted the synthesis of dinuclear 

Au(I) alkynyls containing bridging ADC ligands by using this 

Figure 1. Molecular structure of L 3 Bu(AuCCPh) 2 showing the 

interaction between pairs of molecules (50% thermal ellipsoids). 

Selected bond lengths (Å) and angles (deg): Au(1)−C(1) 2.017(4), 

Au(1)−C(2) 1.988(5), C(2)−C(3) 1.215(6), Au(2)−C(4) 2.021(5), 

Au(2)−C(5) 1.986(5), C(5)−C(6) 1.201(6), Au(3)−C(51) 2.028(5), 

Au(3)−C(52) 1.989(5), C(52)−C(53) 1.207(6), Au(4)−C(54) 

2.017(4), Au(4)−C(55) 1.996(5), C(55)−C(56) 1.204(6), Au(1)− 

Au(4) 3.3898(4); C(2)−Au(1)−C(1) 174.58(18), C(5)−Au(2)− 

C(4) 177.78(19), C(52)−Au(3)−C(51) 178.40(19), C(55)−Au(4)− 

C(54) 177.43(18). 

Scheme 4 

unit. The appearance and λ max values of the spectra are similar 

The structure of L 3 Bu(AuCCPh) 2 shows aurophilic 

method. Thus, compound L 3 *Au 2 Cl 2 was prepared from interactions between two gold atoms of adjacent molecules 

[AuCl(SMe 2 )], tert-butylisocyanide, and N,N′-diethylpropylenediamine 

(Scheme 4), and its X-ray crystal structure was 

determined (Figure 2). However, the reactions of L 3 *Au 2 Cl 2 

with BpylCCH by using several base/solvent combinations 

(Figure 1). The Au−Au distance is 3.3898(4) Å, and the two 

mutually interacting molecules are independent, differing 

mainly in the conformation of the n Bu chains. The structure 

of L 3 *Au 2 Cl 2 (Figure 2) shows three independent molecules, 

(NEt 3 /CD 2 Cl 2 , K 2 CO 3 /CD 2 Cl 2 or CD 3 COCD 3 , KO t Bu/ which present small differences in their conformation. No 

CD 2 Cl 2 , NaOH/THF) gave mixtures that could not be 

separated and characterized. The “acac” method or the reaction 

between [Au(CCBpyl)(CN t Bu)] and MeHN(CH 2 ) 6 NHMe 

in a 2:1 molar ratio gave also inseparable mixtures. 

Crystal Structures. The crystal structures of L 3 Bu(AuC 

CPh) 2 and L 3 *Au 2 Cl 2 were determined by single-crystal X-ray 

diffraction. The coordination geometry is linear in both cases 

aurophilic contacts were observed in this case (the shortest 

Au−Au distance is 5.116 Å), which could be attributed to the 

bulk of the dicarbene ligand. 

Electronic Absorption Spectroscopy. Complexes 

L n R(AuCCR′) 2 display absorption bands in the high-energy 

region (Tables 2 and 3 and Figure 3) with λ max values (λ max ≤ 

242 nm) similar to those shown by L n RAu 2 Cl 2 (Table 1) or 

(C−Au−X in the range 174.58−178.95°). The Au−C carbene and L Me AuCl 51 (234 and 247 nm). Hence, these bands are 

Au−C alkynyl bond distances (2.017−2.028 and 1.986−1.996 Å, 

respectively) are comparable to those found in alkynyl(NHC) 

gold(I) complexes, 20,21,24−26,28,53 whereas the Au−C carbene and 

tentatively assigned to transitions located mainly on the 

gold−carbene unit. In addition, all the alkynyl complexes 

studied, except L 3 R(AuCCC 6 H 4 NO 2 -4) 2 (R = Bz or n Bu), 

Au−Cl bond distances of L 3 *Au 2 Cl 2 (2.003−2.015 and give intense absorptions in the range 257−332 nm with 

2.2821−2.3012 Å) are comparable to their homologues in 

reported chloro(ADC) gold(I) complexes. 54 energies depending mainly on the substituent of the alkynyl 

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Figure 2. Molecular structure of L 3 *Au 2 Cl 2 (50% thermal ellipsoids). 

Selected bond lengths (Å) and angles (deg): Au(1)−C(1) 2.015(4), 

Au(1)−Cl(1) 2.3012(10), Au(2)−C(5) 2.004(4), Au(2)−Cl(2) 

2.2834(10); C(1)−Au(1)−Cl(1) 178.85(12), C(5)−Au(2)−Cl(2) 

178.95(12). 

Table 1. Electronic Absorption and Luminescence Data of 

L n RAu 2 Cl 2 

absorption a luminescence b 

λ abs /nm (ε/10 4 dm 3 mol −1 

complex 

cm −1 ) 

L 1 BzAu 2 Cl 2 230 (1.33), 237 (1.38), 

251 (1.59) 

λ exc / 

nm medium λ em/nm [τ/ 

μs] 

365 solid 438 

273 n PrCN 409 

glass 

L 3 BzAu 2 Cl 2 229 (1.70, sh), 236 (1.84), 

249 (1.95) 

322 solid 432 [0.96, 

5.07] 

270 n PrCN 408 

glass 

L 1 BuAu 2 Cl 2 230 (2.89), 236 (2.89), 315 solid 423 

250 (3.19) 

271 n PrCN 409 

glass 

L 3 BuAu 2 Cl 2 234 (1.49), 248 (1.64) 330 solid 441 [1.05, 

7.23] 

275 n PrCN 350, 420 

glass 

L 3 MeAu 2 Cl 2 235 (1.87), 247 (1.91) 320 solid 452, 611 

270 n PrCN 408 

glass 

L 5 MeAu 2 Cl 2 228 (3.0), 233 (2.93), 322 solid 429 

248 (3.09) 

270 n PrCN 408 

glass 

a Measured in CH 2 Cl 2 solution (2.1 × 10 −5 to 2.4 × 10 −5 M) at 298 K. 

b Measured in the solid state (T = 298 K) or glassy butyronitrile 

solution (1 × 10 −6 to 1.8 × 10 −6 M; T = 77 K). 

to those of gold(I) alkynyls containing phosphine or isocyanide 

ligands, some examples being [Au(CCPh)(PCy 3 )] (λ max = 

290 nm), 55 [Au(CCPh)(PPh 3 )] (284 nm), 56 [Au(C 

CBpyl)(PEt 3 )] (316 nm), 47 [Au 2 (CCPh) 2 (μ-dppe)] (284 

nm), 56 or [Au(CCPh)(CNC 6 H 3 Me 2 -2,6)] (288, 274 nm). 

Therefore, taking into account previous studies, 5,55 we 

tentatively propose these absorptions to be mostly of 

intraligand (IL) [π→π*](CC orCCAr) character with 

some participation of Au orbitals. Accordingly, the shifts to 

lower energies on varying the alkynyl substituent (the λ max 

value of the lowest-energy maximum increases in the order t Bu 

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≈ Me 3 Si < 4-X-C 6 H 4 (X = H, MeO, CF 3 ) ≈ Pyl < Bpyl) may 

be attributed to the increase in π-electron delocalization. 

Compounds L 1 Bz(AuCCPh) 2 and L n Bu(AuCC t Bu) 2 (n =1 

or 3) display weak absorptions in the 318−330 nm region, 

which could not be assigned. 

The low-energy region of the spectra of L 3 R(AuC 

CC 6 H 4 NO 2 -4) 2 (R = Bz or n Bu; Figure 7) is dominated by a 

strong band at 346 or 347 nm (CH 2 Cl 2 ), respectively. This 

absorption shows a modest solvatochromism (for R = n Bu, λ max 

is 345 or 350 nm in toluene or butyronitrile, respectively) and 

is tentatively assigned to a IL [π→π*] transition involving goldperturbed 

states located in the CCC 6 H 4 NO 2 unit. The redshift 

of this absorption with respect to its homologues in the 

remaining phenylethynyl complexes is attributed to some 

charge-transfer character induced by the nitro group. The 

phosphine counterparts [Au(CCC 6 H 4 NO 2 -4)(PR 3 )] (R = 

Cy or Ph) give a band with similar λ max values (336 and 340 

nm, respectively), which has been assigned to an intraligand 

charge-transfer (ILCT) transition. 57 

Luminescence. Complexes L n RAu 2 Cl 2 . Previous studies 23,51 

have reported that complexes of the type [AuCl(NHC)] (NHC 

= 1,3-dimethylimidazol-2-ylidene, 1,3-dimethyltriazol-2-ylidene, 

or 1,3-dimethylbenzimidazol-2-ylidene) give two bands in the 

solid state, with emission maxima in the ranges 410−435 and 

580−650 nm, which were assigned to IL(NHC) and Au···Au 

excited states, respectively. Similarly, solid biscarbene complexes 

L n RAu 2 Cl 2 give an emission with λ max in the range 423− 

452 nm (Table 1 and Figure S1). These bands are broad at 

room temperature, but in glassy butyronitrile display shoulders 

indicating vibronic structure (Figure S2). In CH 2 Cl 2 at 298 K 

they do not emit. Considering the structured character, the 

microsecond lifetimes, and the close similarity of these bands 

with the high-energy bands of their mononuclear counterparts, 

23,51 they are assigned to gold-perturbed 3 IL(NHC) states. 

Additionally, solid L 3 MeAu 2 Cl 2 shows a broad structureless band 

at 611 nm, which is attributable to a Au···Au emission. The 

presence of aurophilic interactions in this complex is not 

surprising considering that L 3 Me is the less bulky ligand of the 

series, being flexible enough to allow an intramolecular Au···Au 

contact, as observed for complex [Au 2 (μ-L 3 Me) 2 ] 2+ . 58 Unfortunately, 

we could not obtain single crystals of L 3 MeAu 2 Cl 2 for an 

X-ray structural confirmation of this assignment. 

Complexes L n R(AuCCR′) 2 (R′ = t Bu or SiMe 3 ). In CH 2 Cl 2 

at 298 K (Table 2), only L 1 R(AuCC t Bu) 2 (R = Bz or n Bu) 

are emissive, giving a broad emisssion around 395 nm and a 

very weak emission around 520 nm (Figure S3). In glassy 

butyronitrile (77 K) their emissions show vibrational structure 

(Figure S4). The solid-state spectra (298 K) of L n R(AuC 

C t Bu) 2 (n =1,R=Bzor n Bu, and n =3,R= n Bu) show a broad 

emission around 450 nm. In contrast, solid L 3 Bz(AuCC t Bu) 2 

(Figure 4) gives a structured emission with λ 0−0 = 413 nm and 

vibronic progressions of 1155, 1516, and 2060 cm −1 , and solid 

L 3 Bu(AuCCSiMe 3 ) 2 (Figure 4) gives a broad emission at 370 

nm and a weak structured emission with λ 0−0 = 423 nm with 

vibronic progressions of 1067, 1517, and 1996 cm −1 . The 

lifetimes of all solid-state emissions are in the microsecond 

range. Considering their Stokes shifts, vibronic progressions, 

and lifetimes, we attribute the solid-state emissions of 

L 3 Bz(AuCC t Bu) 2 and L 3 Bu(AuCCSiMe 3 ) 2 (low-energy 

emission) to gold-perturbed 3 [π→π*](CC) states. For the 

other emissions, a gold-perturbed IL(NHC) character is 

tentatively assigned. Although the differences between the 

solution and solid-state spectra of L 1 R(AuCC t Bu) 2 (R = Bz 

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Table 2. Electronic Absorption and Luminescence Data of L n R(AuCCR′) 2 (R′ = t Bu or Me 3 Si) 

absorption a 

luminescence b 

complex λ abs /nm (ε/10 4 dm 3 mol −1 cm −1 ) 

λ exc / 

nm medium λ em /nm [τ/μs] 

L 1 Bz(AuCC t Bu) 2 240 (2.03, sh), 264 (2.62), 318 (0.24), 330 (0.22) 350 solid 451 [0.70, 6.80] 

350 CH 2 Cl 2 395, 522 (weak) 

350 n PrCN glass 415, 485 (sh) 

L 3 Bz(AuCC t Bu) 2 240 (1.97, sh), 261 (2.99) 280 solid 416, 437, 444, 455 [191.8] 

CH 2 Cl 2 nonemissive 

n PrCN glass nonemissive 

L 1 Bu(AuCC t Bu) 2 240 (2.46, sh), 263 (4.41), 330 (0.16, sh) 350 solid 446 [0.73, 5.34] 

350 CH 2 Cl 2 394, 517 (weak) 

350 n PrCN glass 415, 430 (sh), 487 (sh) 

L 3 Bu(AuCC t Bu) 2 240 (2.82, sh), 261 (4.88), 325 (0.05, sh) 350 solid 455 [0.85, 4.88] 


270 n PrCN glass 360, 443 

L 3 Bu(AuCCSiMe 3 ) 2 242 (2.00, sh), 262 (2.95) 300 solid 370 [0.37, 1.01], 423 (weak), 443 (sh), 452 (sh), 462 (sh) 


270 n PrCN glass 364, 421 (sh) 

a Measured in CH 2 Cl 2 solution (ca. 2 × 10 −5 M) at 298 K. b Measured in the solid state (T = 298 K), deoxygenated CH 2 Cl 2 solution (ca. 2 × 10 −5 M; 

T = 298 K) or glassy butyronitrile solution (1.3 × 10 −6 to 2.2 × 10 −6 M; T = 77 K). 

Table 3. Electronic Absorption and Luminescence Data of L n R(AuCCR′) 2 (R′ = Aryl, Pyl, or Bpyl) 

absorption a 

luminescence b 

compound λ abs /nm (ε/10 4 dm 3 mol −1 cm −1 ) 

λ exc / 

nm medium λ em /nm [τ/μs] 

L 1 Bz(AuCCPh) 2 238 (4.40), 265 (4.20, sh), 274 (4.30), 284 (4.30) 350 solid 477, 510 

350 CH 2 Cl 2 460, 530 

L 3 Bz(AuCCPh) 2 239 (3.70), 260 (3.50, sh), 272 (4.00), 283 (4.13) 350 solid 464 (sh), 503 [0.56, 2.28] 

300 CH 2 Cl 2 421, 448 

290 2-Me-THF glass 419 [202.7], 438, 449, 459 

L 1 Bu(AuCCPh) 2 236 (4.79), 274 (4.48), 284 (4.92), 320 (0.30, sh) 350 solid 410 (sh), 430 (sh), 459, 505 [0.45, 

1.87] 

270 CH 2 Cl 2 305, 420, 440 

270 n PrCN glass 415 [270.8], 435, 444, 456 

L 3 Bu(AuCCPh) 2 238 (3.09), 259 (2.67, sh), 273 (3.59), 283 (3.92) 350 solid 460 (sh), 516 [0.45, 1.69] 

350 CH 2 Cl 2 451, 530 (sh) 

290 2-Me-THF glass 419 [211.5], 438, 448, 460 

L 5 Me(AuCCPh) 2 238 (3.20), 257 (2.52, sh), 272 (3.35), 283 (3.62) 350 solid 416, 496, 539 [96.2], 575 (sh) 

270 CH 2 Cl 2 421, 445, 457 (sh) 

L 3 Bu(AuCCC 6 H 4 CF 3 - 238 (3.31), 260 (2.97, sh), 279 (5.27), 289 (6.10) 315 solid 432, 453 (sh), 471 (sh), 491 (sh) 

4) 2 270 CH 2 Cl 2 432, 452 

290 2-Me-THF glass 429 [249.5], 451, 460, 471 

L 3 Bu(AuCCC 6 H 4 OMe- 238 (3.60), 263 (3.18, sh), 273 (3.83, sh), 284 (4.35), 296 (3.50, 

4) 2 sh) 

360 solid 435 (sh), 477, 494 

275 CH 2 Cl 2 427, 465 

275 n PrCN glass 422, 439, 452, 465 

L 3 Bu(AuCCPyl) 2 238 (3.83), 258 (3.35, sh), 276 (4.43), 282 (4.21, sh) 365 solid 438 (sh), 506 

300 CH 2 Cl 2 430, 454 

290 2-Me-THF glass 424 [193.9], 444, 454, 467 

L 3 Me(AuCCBpyl) 2 236 (3.31), 242 (3.33), 250 (2.87, sh), 319 (6.31), 332 (6.10) 350 solid 400, 507, 549 [17.0, 61.7], 585 (sh) 

350 CH 2 Cl 2 376, 393, 412, 430 (sh), 502, 533 

L 5 Me(AuCCBpyl) 2 235 (4.34), 241 (4.22), 250 (3.19, sh), 319 (7.87), 331 (7.62) 350 solid 413, 505, 549, 585 (sh) 

350 CH 2 Cl 2 376, 394, 408 (sh), 507, 536 

L 3 Bz(AuCCC 6 H 4 NO 2 - 236 (4.43), 346 (4.81) 350 solid 462, 528, 557 (sh) 

4) 2 CH 2 Cl 2 nonemissive 

360 n PrCN glass 413 (weak), 501, 536 

L 3 Bu(AuCCC 6 H 4 NO 2 - 234 (2.95), 347 (3.05) 350 solid 453, 524, 547 (sh) 

4) 2 CH 2 Cl 2 nonemissive 

365 2-Me-THF glass 502 [412.4], 537 

a Measured in CH 2 Cl 2 solution (1.9 × 10 −5 to 2.5 × 10 −5 M) at 298 K. b Measured in the solid state (T = 298 K), deoxygenated CH 2 Cl 2 solution (1.9 

× 10 −5 to 2.5 × 10 −5 M; T = 298 K) or glassy 2-methyltetrahydrofuran or butyronitrile solution (1.3 × 10 −6 to 2 × 10 −6 M; T = 77 K). 

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Figure 3. Absorption spectra (CH 2 Cl 2 ) of selected L n R(AuCCR′) 2 

complexes. 

Figure 6. Emission spectra of L 3 Me(AuCCBpyl) 2 (298 K). 

Figure 4. Emission spectra (298 K) of solid L 3 Bz(AuCC t Bu) 2 

(continuous line) and L 3 Bu(AuCCSiMe 3 ) 2 (dashed line). 

Figure 5. Excitation (dashed line) and emission (continuous line) 

spectra of L 3 Bu(AuCCR′) 2 [R′ = Ph (gray) or 3-pyridyl (black)] 

measured in glassy 2-methyltetrahydrofuran at 77 K. 

or n Bu) suggest the influence of intra- or intermolecular 

interactions, we have no structural evidence for these 

Figure 7. Absorption (continuous line), excitation (77 K, λ em = 500 

nm, dashed line), and emission spectra (77 K, λ exc = 350 nm, dashdotted 

line) of L 3 Bu(AuCCC 6 H 4 NO 2 -4) 2 . All were measured in 

butyronitrile. 

interactions because we could not obtain single crystals suitable 

for X-ray diffraction after repeated attempts. 

Complexes L n R(AuCCR′) 2 (R′ = Aryl, Pyridyl, or Bipyridyl). 

Complexes L n R(AuCCPh) 2 (n = 1 or 3, R = n Bu or Bz; n =5, 

R = Me), L 3 Bu(AuCCC 6 H 4 X-4) 2 (X = CF 3 or OMe), and 

L 3 Bu(AuCCPyl) 2 are emissive at 298 K in CH 2 Cl 2 solution 

and in the solid state (Table 3 and Figures S5−S8). The 

emission maxima are in the range 420−539 nm, and the 

vibrational structure is poorly resolved. However, in glassy 

solutions of butyronitrile or 2-methyltetrahydrofuran at 77 K, 

they give a sharp structured emission (Figure 5) with λ 0−0 in 

the range 415−427 nm and vibronic spacings of ca. 1100, 1550, 

and 2100 cm −1 . Under these conditions, the excitation spectra 

(Figure 5) match the lower-energy absorptions (Figure 3), and 

lifetimes in the microsecond range could be determined. The 

large Stokes shifts, vibronic progressions, and lifetimes suggest a 

gold-perturbed intraligand 3 [π→π*](CC or CCAr) 

character for the emitting states. 5,23,28 Similar emission 

wavelengths and vibronic spacings have been reported for 

their phosphine or isocyanide counterparts, examples being 

[Au(CCPh)(PCy 3 )] (λ 0−0 = 419 nm), 55 [Au(CCPh)- 

(PPh 3 )] (419 nm), 56 [Au 2 (CCPh) 2 (μ-dppe)] (420 nm), 56 

or [Au(CCPh)(CNC 6 H 3 Me 2 -2,6)] (419 nm). 33 The bipyridylethynyl 

compounds L n Me(AuCCBpyl) 2 (n = 3 or 5) gave 

5419 



dual emissions at 298 K in CH 2 Cl 2 solution and in the solid 

state (Figure 6), with maxima in the ranges 376−412 and 505− 

585 nm. Since these emissions closely resemble those of their 

diphosphine counterparts, 47,59 they were similarly attributed to 

intraligand [π→π*](AuCCBpyl) fluorescence (high-energy 

emission) and phosphorescence (low-energy emission). 

The emission maximum of L 3 Bu(AuCCPh) 2 in the solid 

state (λ max = 516 nm) is shifted to lower energies with respect 

to the solution spectrum (λ max = 451 nm). As this compound 

shows intermolecular short Au···Au contacts in its crystal 

structure (Figure 1), this red-shift is attributed to a perturbation 

of the emitting state originated by the aurophilic interaction. 

Similar red-shifts (Δλ max = 55−76 nm) were observed for 

L 3 Bz(AuCCPh) 2 , L 3 Bu(AuCCPyl) 2 , and L 5 Me(AuC 

CPh) 2 . 

Finally, the 4-nitrophenylethynyl compounds L 3 R(AuC 

CC 6 H 4 NO 2 -4) 2 (R = n Bu or Bz) are not emissive in CH 2 Cl 2 

solution at 298 K, and they are weakly emissive in the solid 

state. However, in butyronitrile glass, they give an emission 

with two maxima, at 500 and 535 nm, the spacing between 

them corresponding to a vibronic progression of ca. 1300 cm −1 

(Figure 7). These emissions resemble that of solid [Au(C 

CC 6 H 4 NO 2 )(PCy 3 )], 57 but differ from that of their phenylethynyl 

counterparts, suggesting that the emissive states of the 

4-nitro-substituted complexes are different from those of the 

other phenylethynyl complexes studied. As the excitation 

maxima of the emissions of L 3 R(AuCCC 6 H 4 NO 2 -4) 2 (350 

or 360 nm for R = n Bu or Bz, respectively) agree with their 

absorption maxima (Figure 7), in accord with previous 

studies, 57 we propose that they originate from gold-perturbed 

IL 3 [π→π*](CCAr) states with some charge-transfer 

character. 

■ SUMMARY 

New gold(I) alkynyls containing NHC ligands have been 

prepared by the following methods: (a) the reaction of in situ 

generated gold(I) acetylacetonato carbene complexes with 

terminal alkynes; (b) the reaction of silver(I) NHC complexes 

with gold(I) acetylides; (c) the reaction of dinuclear gold(I) 

chloro carbenes with terminal alkynes in the presence of a base. 

Methods (a) and (b) have been used for the first time in the 

synthesis of NHC gold complexes. The first dinuclear alkynyl 

gold(I) complexes containing bridging dicarbene ligands have 

been prepared, and their photophysical properties have been 

studied. The lower-energy bands of their absorption spectra 

have been assigned to gold-perturbed intraligand [π→π*](C 

C or CCAr) transitions. The new dinuclear chloro 

complexes are luminescent at room temperature in the solid 

state, and their emissions are similar to those of their 

mononuclear counterparts. Most of the dinuclear alkynyl 

complexes are luminescent at room temperature, in particular 

those derived from aryl- or heteroarylalkynes, the emissive 

behavior of which resembles that of their phosphine analogues. 

Thus, they show structured emissions with lifetimes in the 

microsecond range, which have been assigned to goldperturbed 

■ 

intraligand 3 [π→π*](CCAr) excited states. 

EXPERIMENTAL SECTION 

General Considerations. L Bz AgBr, 52 L Me AuCl, 51 [Au(CCR)] n 

(R = Ph or t Bu), 60 and the alkynes HCCR (R = 4-C 6 H 4 NO 61 2 and 

Bpyl 62 ) were prepared using reported methods. HPLC-grade solvents 

were used as received unless otherwise stated. When necessary, 

CH 2 Cl 2 was previously distilled over calcium hydride and stored under 

5420 

Article 

nitrogen. Infrared spectra were recorded in the range 4000−200 cm −1 

on a Perkin-Elmer 16F PC FT-IR spectrometer using KBr pellets. C, 

H, N, and S analyses were carried out with Carlo Erba 1108 and 

LECO CHS-932 microanalyzers. NMR spectra were measured on 

Bruker Avance 200, 300, and 400 instruments. 1 H chemical shifts were 

referenced to residual CHCl 3 (7.26 ppm) or d 5 -DMSO (2.50 ppm). 

13 C{ 1 H} and 19 F NMR spectra were referenced to CDCl 3 (77.1 ppm) 

and to external CFCl 3 , respectively. Abbreviations used: br (broad), sh 

(shoulder), q (quartet), quint (quintet), sext (sextet), Im (imidazole). 

Assignments of 1 H and 13 C{ 1 H} NMR spectra are based on COSY, 

HMQC, and HMBC experiments. In the experimental data, the 

imidazole rings are numbered as shown in Scheme 2. Melting points 

were determined on a Reichert apparatus in the open air. UV−visible 

absorption spectra were recorded on a Perkin-Elmer Lambda 750S 

spectrometer in 1 cm path length quartz cuvettes. Steady-state 

excitation and emission spectra were measured on a Jobin Yvon 

Fluorolog 3-22 spectrofluorimeter with a 450 W xenon lamp, doublegrating 

monochromators, and a Hamamatsu R-928P photomultiplier. 

The solutions for luminescence measurements were deoxygenated by 

bubbling N 2 and placed inside 1 cm path length quartz fluorescence 

cuvettes (298 K) under a N 2 atmosphere. Low-temperature (77 K) 

emission measurements were carried out in quartz tubes using an 

optical Dewar sample holder filled with liquid N 2 . The solid samples 

were placed between quartz coverslips. Phosphorescence lifetimes 

were measured using an incorporated Jobin Yvon FL-1040 

phosphorimeter or by time-correlated single-photon counting on a 

FluoroHub of IBH with pulsed diodes (NanoLed) as excitation 

sources (λ exc = 334 or 372 nm). 

Synthesis of the Diimidazolium Salts. Diimidazolium salts 

(L n RH 2 )Br 2 (R = Bz, n =1 37 or 3; 38 R= n Bu, n =1 39 or 3; 40 R = Me, n 

=3 41 or 5 42 ) were prepared using a modified literature method. 63 A 

THF solution of 1-(benzyl, n-butyl, or methyl)-1H-imidazole and the 

corresponding Br(CH 2 ) n Br (2:1 molar ratio) was stirred at 100 °C 

overnight in a Carius tube. The precipitated salts were filtered, washed 

with Et 2 O, and dried under vacuum. The yields were nearly 

quantitative, and their NMR data agree with those previously reported. 

Synthesis of Silver(I) Biscarbene Complexes. All complexes 

have been prepared by reaction of the bisimidazolium salt with an 

equimolar amount of Ag 2 O in acetonitrile. The resulting suspension 

was stirred overnight at room temperature in the dark. The light gray 

solids were isolated by filtration, washed with Et 2 O(3× 5 mL), and 

dried under vacuum. The obtained compounds are soluble only in 

highly polar solvents such as DMSO, and their NMR spectra show 

only the expected signals for the carbene ligand. They were used for 

the synthesis of the gold complexes without further purification. 

L 1 BzAg 2 Br 2 . This was prepared from (L 1 BzH 2 )Br 2 (521 mg, 1.06 

mmol) and Ag 2 O (246 mg, 1.06 mmol). Yield: 724 mg, 1.03 mmol, 

97%. The 1 H and 13 C{ 1 H} NMR of the compound spectra agree with 

those reported. 43 

L 3 BzAg 2 Br 2 . This was prepared from (L 3 BzH 2 )Br 2 (230 mg, 0.44 


89%. Anal. Calcd for C 23 H 24 N 4 Ag 2 Br 2 : C, 37.74; H, 3.30; N, 7.65. 

Found: C, 37.74; H, 3.41; N, 7.64. 1 H NMR (400.9 MHz, d 6 -DMSO): 

δ 7.58 (s, 4H, CH, Im), 7.33−7.24 (m, 10H, Ph), 5.25 (s, 4H, 

PhCH 2 ), 4.04 (t, 4H, CH 2 CH 2 N, 3 J HH = 6.1 Hz), 2.39 (quint, 2H, 

CH 2 CH 2 N, 3 J HH = 6.1 Hz). 13 C{ 1 H} NMR (100.8 MHz, d 6 -DMSO): 

δ 179.8 (C2, Im), 137.0 (C1, Ph), 128.7, (Ph), 128.0 (C4, Ph), 127.6 

(Ph), 123.0 (CH, Im), 121.4 (CH, Im), 54.2 (PhCH 2 ), 47.6 

(CH 2 CH 2 N), 30.5 (CH 2 CH 2 N). 

L 1 BuAg 2 Br 2 . This was prepared from (L 1 BuH 2 )Br 2 (131 mg, 0.31 



Found: C, 26.45; H, 3.59; N, 8.10. The element ratios agree with those 

of the ligand, and the NMR spectra show only the expected signals for 

the ligand; therefore the low percentages are attributed to inorganic 

silver impurities, which do not affect its use as carbene-transfer reagent. 

1 H NMR (400.9 MHz, d 6 -DMSO): δ 7.83 (d, 2H, CH, Im, 3 J HH = 1.5 

Hz), 7.61 (d, 2H, CH, Im, 3 J HH = 1.4 Hz), 6.67 (s, 2H, NCH 2 N), 4.12 

(t, 4H, H1, n Bu, 3 J HH = 7.2 Hz), 1.73 (quint, 4H, H2, n Bu, 3 J HH = 7.2 

Hz), 1.22 (sext, 4H, H3, n Bu, 3 J HH = 7.2 Hz), 0.83 (t, 6H, Me, 3 J HH = 



7.2 Hz). 13 C{ 1 H} NMR (75.5 MHz, d 6 -DMSO): δ 180.9 (C2, Im), 

122.7 (C4, Im), 121.7 (C5, Im), 63.3 (NCH 2 N), 51.2 (C1, n Bu), 33.0 

(C2, n Bu), 19.2 (C3, n Bu), 13.5 (Me). 

L 3 BuAg 2 Br 2 . This was prepared from (L 3 BuH 2 )Br 2 (680 mg, 1.51 



Found: C, 28.86; H, 3.96; N, 7.77. The element ratios agree with those 

of the ligand, and the NMR spectra show only the expected signals for 

the ligand; therefore the low percentages are attributed to inorganic 

silver impurities, which do not affect its use as carbene-transfer reagent. 

1 H NMR (400.9 MHz, d 6 -DMSO): δ 7.58 (d, 2H, CH, Im, 3 J HH = 1.6 

Hz), 7.57 (d, 2H, CH, Im, 3 J HH = 1.6 Hz), 4.02 (t, 4H, CH 2 CH 2 N, 

3 J HH = 5.6 Hz), 3.95 (t, 4H, H1, n Bu, 3 J HH = 7.3 Hz), 2.44 (quint, 2H, 

CH 2 CH 2 N, 3 J HH = 5.6 Hz), 1.70 (quint, 4H, H2, n Bu, 3 J HH = 7.2 Hz), 

1.22 (sext, 4H, H3, n Bu, 3 J HH = 7.2 Hz), 0.85 (t, 6H, Me, 3 J HH = 7.2 

Hz). 13 C{ 1 H} NMR (100.8 MHz, d 6 -DMSO): δ 179.3 (C2, Im), 122.6 

(CH, Im), 121.0 (CH, Im), 50.6 (C1, n Bu), 47.1 (CH 2 CH 2 N), 32.9 

(C2, n Bu), 30.2 (CH 2 CH 2 N), 19.2 (C3, n Bu), 13.4 (Me). 

L 3 MeAg 2 Br 2 . This was prepared from (L 3 MeH 2 )Br 2 (554 mg, 1.51 


91%. Anal. Calcd for C 11 H 16 N 4 Ag 2 Br 2·(CH 3 CN) 0.4 : C, 23.77; H, 2.91; 

N, 10.34. Found: C, 23.95; H, 2.87; N, 10.63. The amount of 

acetonitrile was estimated from the elemental analyses and 

corroborated by integration of the 1 H NMR spectrum. 1 H NMR 

(400.9 MHz, d 6 -DMSO): δ 7.60 (d, 2H, CH, Im, 3 J HH = 1.6 Hz), 7.52 

(d, 2H, CH, Im, 3 J HH = 1.6 Hz), 3.95 (t, 4H, CH 2 CH 2 N, 3 J HH = 5.8 

Hz), 3.64 (s, 6H, Me), 2.45 (quint, 2H, CH 2 CH 2 N, 3 J HH = 5.8 Hz), 

2.04 (s, 1.2H, MeCN). 13 C{ 1 H} NMR (75.5 MHz, d 6 -DMSO): δ 

180.0 (C2, Im), 124.0 (C4, Im), 120.8 (C5, Im), 46.6 (CH 2 CH 2 N), 

37.9 (Me), 29.5 (CH 2 CH 2 N), 1.2 (MeCN); the MeCN signal was not 

detected. 

L 5 MeAg 2 Br 2 . This was prepared from (L 5 MeH 2 )Br 2 (706 mg, 1.79 

mmol) and Ag 2 O (415 mg, 1.79 mmol). Yield: 883.5 mg, 1.45 mmol, 

81%. The 1 H and 13 C{ 1 H} NMR spectra of the compound agree with 

those reported. 42 

L 1 BzAu 2 Cl 2 . [AuCl(SMe 2 )] (142 mg, 0.48 mmol) was added to a 

suspension of L 1 BzAg 2 Br 2 (170 mg, 0.24 mmol) in CH 2 Cl 2 (10 mL). 

The mixture was stirred for 15 h at room temperature in the dark and 

filtered through Celite. The filtrate was concentrated under vacuum to 

ca. 1 mL. Addition of Et 2 O (30 mL) gave a white precipitate, which 

was filtered, washed with Et 2 O(3× 5 mL), and dried under vacuum. 

Yield: 159 mg, 0.20 mmol, 84%. Mp: 182 °C dec. Anal. Calcd for 

C 21 H 20 N 4 Au 2 Cl 2 : C, 31.80; H, 2.54; N, 7.06. Found: C, 31.43; H, 2.24; 

N, 6.95. 1 H NMR (400.9 MHz, CDCl 3 ): δ 7.85 (d, 2H, CH, Im, 3 J HH 

= 2.0 Hz), 7.40−7.37 (m, 6H, Ph), 7.33−7.31 (m, 4H, Ph), 6.94 (d, 

2H, CH, Im, 3 J HH = 2.0 Hz), 6.46 (s, 2H, NCH 2 N), 5.36 (s, 4H, 

CH 2 Ph). 13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): δ 172.1 (C2, Im), 

133.9 (C1, Ph), 129.3 (Ph), 129.2 (C4, Ph), 128.2 (Ph), 121.8 (CH, 

Im), 121.6 (CH, Im), 63.1 (NCH 2 N), 55.7 (PhCH 2 ). 

L 3 BzAu 2 Cl 2 . This was prepared in the same way as L 1 BzAu 2 Cl 2 

starting from L 3 BzAg 2 Br 2 (137 mg, 0.19 mmol) and [AuCl(SMe 2 )] 

(110 mg, 0.37 mmol). Yield: 129 mg, 0.16 mmol, 83%. Mp: 196 °C. 

Anal. Calcd for C 23 H 24 N 4 Au 2 Cl 2·(H 2 O) 0.13 : C, 33.54; H, 2.97, N, 6.80. 

Found: C, 33.13; H, 2.74; N, 6.90. The amount of water was estimated 

from the elemental analyses and corroborated by integration of the 1 H 

NMR spectrum. 1 H NMR (400.9 MHz, CDCl 3 ): δ 7.35 (br s, Ph, 

10H), 7.05 (d, 2H, H5, Im, 3 J HH = 1.9 Hz), 6.91 (d, 2H, H4, Im, 3 J HH 

= 1.9 Hz), 5.36 (s, 4H, CH 2 Ph), 4.25 (t, 4H, CH 2 CH 2 N, 3 J HH = 6.6 

Hz), 2.50 (quint, 2H, CH 2 CH 2 N, 3 J HH = 6.6 Hz), 1.57 (s, 0.26H, 

H 2 O). 13 C{ 1 H} NMR (100.1 MHz, CDCl 3 ): δ 171.4 (C2, Im), 134.9 

(C1, Ph), 129.1 (Ph), 128.7 (C4, Ph), 128.3 (Ph), 121.7 (C4, Im), 

119.9 (C5, Im), 55.3 (PhCH 2 ), 47.3 (CH 2 CH 2 N), 30.4 (CH 2 CH 2 N). 

L 1 BuAu 2 Cl 2 . This was prepared in the same way as L 1 BzAu 2 Cl 2 

starting from L 1 BuAg 2 Br 2 (178 mg, 0.28 mmol) and [AuCl(SMe 2 )] 

(173 mg, 0.59 mmol). Yield: 165 mg, 0.23 mmol, 81%. Mp: 161 °C 

dec. Anal. Calcd for C 15 H 24 N 4 Au 2 Cl 2 : C, 24.84; H, 3.34; N, 7.73. 

Found: C, 24.44; H, 3.15; N, 7.50. 1 H NMR (300.1 MHz, CDCl 3 ): δ 

7.85 (d, 2H, H5, Im, 3 J HH = 1.8 Hz), 7.00 (d, 2H, H4, Im, 3 J HH = 1.8 

Hz), 6.42 (s, 2H, NCH 2 N), 4.18 (t, 4H, H1, n Bu, 3 J HH = 7.2 Hz), 1.84 

(quint, 4H, H2, n Bu, 3 J HH = 7.2 Hz), 1.37 (m, 4H, H3, n Bu, 3 J HH = 7.2 

Article 

Hz), 0.96 (t, 6H, Me, 3 J HH = 7.2 Hz). 13 C{ 1 H} NMR (100.8 MHz, 

CDCl 3 ): δ 171.6 (C2, Im), 121.6 (C4, Im), 121.3 (C5, Im), 63.0 

(NCH 2 N), 51.8 (C1, n Bu), 32.8 (C2, n Bu), 19.6 (C3, n Bu), 13.6 (Me). 

L 3 BuAu 2 Cl 2 . This was prepared in the same way as L 1 BzAu 2 Cl 2 

starting from L 3 BuAg 2 Br 2 (321 mg, 0.48 mmol) and [AuCl(SMe 2 )] 

(285 mg, 0.97 mmol). Yield: 301 mg, 0.40 mmol, 84%. Mp: 151−152 

°C. Anal. Calcd for C 17 H 28 N 4 Au 2 Cl 2 : C, 27.11; H, 3.75; N, 7.44. 

Found: C, 26.88; H, 3.58; N, 7.69. 1 H NMR (400.9 MHz, CDCl 3 ): δ 

7.10 (d, 2H, CH, Im, 3 J HH = 2.0 Hz), 7.03 (d, 2H, CH, Im, 3 J HH = 2.0 

Hz), 4.22 (t, 4H, CH 2 CH 2 N, 3 J HH = 6.8 Hz), 4.20 (t, 4H, H1, n Bu, 

3 J HH = 7.4 Hz), 2.50 (quint, 2H, CH 2 CH 2 N, 3 J HH = 6.8 Hz), 1.83 

(quint, 4H, H2, n Bu, 3 J HH = 7.2 Hz), 1.36 (sext, 4H, H3, n Bu, 3 J HH = 

7.2 Hz), 0.96 (t, 6H, Me, 3 J HH = 7.2 Hz). 13 C{ 1 H} NMR (50.3 MHz, 

CDCl 3 ): δ 170.6 (C2, Im), 121.6 (CH, Im), 120.0 (CH, Im), 51.5 

(C1, n Bu), 47.6 (CH 2 CH 2 N), 32.9 (C2, n Bu), 31.3 (CH 2 CH 2 N), 19.7 

(C3, n Bu), 13.6 (Me). 

L 3 MeAu 2 Cl 2 . [AuCl(SMe 2 )] (99 mg, 0.34 mmol) was added to a 

suspension of L 3 MeAg 2 Br 2 (98 mg, 0.17 mmol) in acetonitrile (15 mL). 

The mixture was stirred overnight at room temperature in the dark 

and filtered. The filtrate was concentrated under vacuum to ca. 1 mL. 

Addition of Et 2 O (20 mL) gave a white precipitate, which was filtered 

off, washed with Et 2 O(3× 5 mL), and dried under vacuum. Next, the 

solid that precipitated in the reaction mixture was stirred with DMSO 

(7 mL), and the suspension was filtered through Celite. The filtrate 

was concentrated under reduced pressure, and Et 2 O (20 mL) was 

added to precipitate a second crop of the same compound, which was 

filtered off, washed with Et 2 O(3× 5 mL), and dried under vacuum. 

Overall yield: 66 mg, 0.10 mmol, 61%. Mp: 167 °C dec. Anal. Calcd 

for C 11 H 16 N 4 Au 2 Cl 2 : C, 19.75; H, 2.41; N, 8.37. Found: C, 19.60; H, 

2.70; N, 8.33. 1 H NMR (400.9 MHz, CDCl 3 ): δ 7.55 (d, 2H, CH, Im, 

3 J HH = 1.9 Hz), 7.48 (d, 2H, CH, Im, 3 J HH = 1.9 Hz), 4.02 (t, 4H, 

CH 2 CH 2 N, 3 J HH = 6.2 Hz), 3.76 (s, 6H, Me), 2.44 (quint, 4H, 

CH 2 CH 2 N, 3 J HH = 6.2 Hz). 13 C{ 1 H} NMR (75.5 MHz, CDCl 3 ): δ 

169.7 (C2, Im), 123.6 (C4, Im), 120.0 (C5, Im), 46.1 (CH 2 CH 2 N), 

37.6 (Me), 28.8 (CH 2 CH 2 N). 

L 5 MeAu 2 Cl 2 . This was prepared in the same way as L 1 BzAu 2 Cl 2 

starting from L 5 MeAg 2 Br 2 (482 mg, 0.79 mmol) and [AuCl(SMe 2 )] 

(515 mg, 1.75 mmol). Yield: 524 mg, 0.75 mmol, 95%. Mp: 77−78 °C. 

Anal. Calcd for C 13 H 20 N 4 Au 2 Cl 2 : C, 22.40; H, 2.89; N, 8.04. Found: C, 

22.21; H, 2.54; N, 7.65. 1 H NMR (200.1 MHz, CDCl 3 ): δ 7.09 (d, 2H, 

CH, Im, 3 J HH = 1.9 Hz), 6.99 (d, 2H, CH, Im, 3 J HH = 1.9 Hz), 4.17 (t, 

4H, CH 2 CH 2 CH 2 N, 3 J HH = 6.9 Hz), 3.86 (s, 6H, Me), 1.89 (quint, 

4H, CH 2 CH 2 CH 2 N, 3 J HH = 6.9 Hz), 1.39 (m, 2H, CH 2 CH 2 CH 2 N). 

13 C{ 1 H} NMR (75.5 MHz, CDCl 3 ): δ 170.6 (C2, Im), 122.2 (CH, 

Im), 120.6 (CH, Im), 50.6 (CH 2 CH 2 CH 2 N), 38.4 (Me), 30.1 

(CH 2 CH 2 CH 2 N), 22.9(CH 2 CH 2 CH 2 N). 

L 1 Bz(AuCCPh) 2 . Method A: To a solution of L 1 BzAu 2 Cl 2 (120 mg, 

0.15 mmol) in dry CH 2 Cl 2 (7 mL) was added Tl(acac) (96 mg, 0.32 

mmol). The white suspension formed was stirred for 10 min and 

filtered through Celite. Then, HCCPh (42 mg, 45 μL, 0.38 mmol) 

was added, and the solution was stirred for 6 h. The reaction mixture 

was filtered through Celite to remove a small amount of colloidal gold 

and concentrated under vacuum to ca. 1 mL. Addition of Et 2 O (30 

mL) gave a white precipitate, which was filtered off, washed with Et 2 O 

(3 × 5 mL), and dried under vacuum. Yield: 122 mg, 0.13 mmol, 88%. 

Method B: To a suspension of L 1 BzAg 2 Br 2 (81 mg, 0.12 mmol) in 

CH 2 Cl 2 (7 mL) was added [AuCCPh] n (77 mg, 0.26 mmol). The 

gray suspension was stirred overnight at room temperature in the dark 

and filtered through Celite. The filtrate was stirred with 

Na 2 S 2 O 3·5H 2 O (0.5 g) for 5 h, filtered through Celite, and 

concentrated under vacuum to ca. 1 mL. Addition of Et 2 O (20 mL) 

gave a white precipitate, which was filtered off, washed with Et 2 O(3× 

5 mL), and dried under vacuum. Yield: 100 mg, 0.11 mmol, 90%. Mp: 

140−142 °C dec. Anal. Calcd for C 37 H 30 N 4 Au 2 : C, 48.06; H, 3.27; N, 

6.06. Found: C, 48.39; H, 3.04; N, 6.17. IR (KBr, cm −1 ): ν(CC) 

2115. 1 H NMR (400.9 MHz, CDCl 3 ): δ 7.81 (d, 2H, H5, Im, 3 J HH = 

1.8 Hz), 7.48 (m, 4H, H2, PhCC), 7.36−7.30 (m, 10H, PhCH 2 ), 

7.24−7.16 (m, 6H, H3 and H4, PhCC), 6.86 (d, 2H, H4, Im, 3 J HH = 

1.9 Hz), 6.58 (s, 2H, NCH 2 N), 5.40 (s, 4H, PhCH 2 ). 13 C{ 1 H} NMR 

(100.8 MHz, CDCl 3 ): δ 187.8 (C2, Im), 134.3 (C1, PhCH 2 ), 132.3 

5421 



(C2, PhCC), 129.2 (C3, PhCH 2 ), 129.0 (C4, PhCH 2 ), 128.2 (C2, 

PhCH 2 ), 127.9 (C3, PhCC), 127.1 (C1, PhCC), 126.7 (C4, 

PhCC), 125.1 (CCAu), 121.6 (C4, Im), 121.6 (C5, Im), 105.8 

(CCAu), 62.6 (NCH 2 N), 55.2 (PhCH 2 ). 

L 1 Bz(AuCC t Bu) 2 . This was prepared in the same way as 

L 1 Bz(AuCCPh) 2 . Method A: From L 1 BzAu 2 Cl 2 (71 mg, 0.090 

mmol), Tl(acac) (57 mg, 0.19 mmol), and HCC t Bu (27 μL, 0.22 

mmol). Yield: 58 mg, 0.066 mmol, 73%. Method B: From L 1 BzAg 2 Br 2 

(117 mg, 0.17 mmol) and [AuCC t Bu] n (92 mg, 0.33 mmol). Yield: 

105 mg, 0.12 mmol, 70%. Mp: 195 °C dec. Anal. Calcd for 

C 33 H 38 N 4 Au 2 : C, 44.81; H, 4.33; N, 6.33. Found: C, 44.54; H, 4.36; N, 

6.26. IR (KBr, cm −1 ): ν(CC) 2116. 1 H NMR (400.9 MHz, CDCl 3 ): 

δ 7.73 (d, 2H, H5, Im, 3 J HH = 2.0 Hz), 7.36−7.25 (m, 10H, Ph), 6.81 

(d, 2H, H4, Im, 3 J HH = 2.0 Hz), 6.58 (s, 2H, NCH 2 N), 5.38 (s, 4H, 

CH 2 Ph), 1.31 (s, 9H, t Bu). 13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): δ 

188.4 (C2, Im), 134.5 (C1, Ph), 129.1 (C3, Ph), 128.9 (C4, Ph), 128.1 

(C2, Ph), 121.4 (C4, Im), 121.3 (C5, Im), 116.1 (CCAu), 111.3 

(CCAu), 62.4 (NCH 2 N), 55.0 (PhCH 2 ), 32.4 (CMe 3 ), 28.3 

(CMe 3 ). 

L 3 Bz(AuCCPh) 2 . Prepared in the same way as L 1 Bz(AuCCPh) 2 . 

Method A: From L 3 BzAu 2 Cl 2 (127 mg, 0.15 mmol), Tl(acac) (99 mg, 

0.33 mmol), and HCCPh (42 μL, 0.39 mmol). Yield: 99 mg, 0.10 

mmol, 69%. Method B: From L 3 BzAg 2 Br 2 (100 mg, 0.14 mmol) and 

[AuCCPh] n (85 mg, 0.29 mmol). Yield: 83 mg, 0.09 mmol, 62%. 

Mp: 143−144 °C. Anal. Calcd for C 39 H 34 N 4 Au 2 : C, 49.17; H, 3.60; N, 

5.88. Found: C, 48.74; H, 3.43; N, 5.87. IR (KBr, cm −1 ): ν(CC) 

2105. 1 H NMR (400.9 MHz, CDCl 3 ): δ 7.50−7.47 (m, 4H, H2, 

PhCH 2 ), 7.33−7.18 (m, 16H, Ph), 7.03 (d, 2H, H5, Im, 3 J HH = 2.0 

Hz), 6.78 (d, 2H, H4, Im, 3 J HH = 2.0 Hz), 5.47 (s, 4H, CH 2 Ph), 4.31 

(t, 4H, CH 2 CH 2 N, 3 J HH = 6.8 Hz), 2.55 (quint, 2H, CH 2 CH 2 N, 3 J HH = 

6.8 Hz). 13 C{ 1 H} NMR (110.8 MHz, CDCl 3 ): δ 187.1 (C2, Im), 

135.3 (C1, CH 2 Ph), 132.2 (C2, PhCC), 129.0 (C3, PhCH 2 ), 128.5 

(C4, PhCH 2 ), 128.3 (C2, PhCH 2 ), 127.9 (C3, PhCC), 126.4 (C4, 

PhCC), 125.7 (CCAu), 121.2 (C4, Im), 120.5 (C5, Im), 105.3 

(CCAu), 55.0 (PhCH 2 ), 47.5 (CH 2 CH 2 N), 31.4 (CH 2 CH 2 N); the 

signal of C1 of PhCC was not detected. 

L 3 Bz(AuCC t Bu) 2 . Prepared in the same way as L 1 Bz(AuC 

CPh) 2 . Method A: From L 3 BzAu 2 Cl 2 (61 mg, 0.074 mmol), Tl(acac) 

(48 mg, 0.16 mmol), and HCC t Bu (23 μL, 0.19 mmol). Yield: 54 

mg, 0.059 mmol, 80%. Method B: From L 3 BzAg 2 Br 2 (138 mg, 0.19 

mmol) and [AuCC t Bu] n (105 mg, 0.38 mmol). Yield: 102 mg, 0.11 

mmol, 59%. Mp: 170 °C dec. Anal. Calcd for: C 35 H 42 N 4 Au 2 : C, 46.06; 

H, 4.64; N, 6.14. Found: C, 45.98; H, 5.00; N, 6.21. IR (KBr, cm −1 ): 

ν(CC) 2112. 1 H NMR (400.9 MHz, CDCl 3 ): δ 7.35−7.25 (m, 

10H, Ph), 7.03 (d, 2H, H5, Im, 3 J HH = 2.0 Hz), 6.67 (d, 2H, H4, Im, 

3 J HH = 2.0 Hz), 5.38 (s, 4H, PhCH 2 ), 4.26 (t, 4H, CH 2 CH 2 N, 3 J HH = 

7.1 Hz), 2.56 (quint, 2H, CH 2 CH 2 N, 3 J HH = 7.1 Hz), 1.30 (s, 9H, 

t Bu). 13 C{ 1 H} NMR (110.8 MHz, CDCl 3 ): δ 187.6 (C2, Im), 135.3 

(C1, Ph), 128.9 (C3, Ph), 128.5 (C4, Ph), 128.1 (C2, Ph), 121.1 (C5, 

Im), 120.5 (C4, Im), 115.7 (CCAu), 112.0 (CCAu), 54.8 

(CH 2 Ph), 47.9 (CH 2 CH 2 N), 32.5 (CMe 3 ), 32.0 (CH 2 CH 2 N), 28.3 

(CMe 3 ). 

L 3 Bz(AuCCC 6 H 4 NO 2 -4) 2 . Method C: To a solution of L 3 BzAu 2 Cl 2 

(180 mg, 0.22 mmol) in acetone (15 mL) were added K 2 CO 3 (69 mg, 

0.50 mmol) and HCCC 6 H 4 NO 2 -4 (65 mg, 0.44 mmol). The 

reaction mixture was stirred for 24 h, and the solvent was removed 

under vacuum. The residue was stirred with 20 mL of CH 2 Cl 2 . After 

filtration through Celite, the solution was concentrated under vacuum 

to ca. 1 mL. Addition of Et 2 O (20 mL) gave a yellow solid, which was 

filtered, washed with Et 2 O(3× 5 mL), and dried under vacuum. Yield: 


C 39 H 32 N 6 Au 2 O 4 : C, 44.93; H, 3.09; N, 8.06. Found: C, 44.97; H, 2.80; 

N, 8.05. IR (KBr, cm −1 ): ν(CC) 2107. 1 H NMR (400.9 MHz, 

CDCl 3 ): δ 8.13−8.10 (m, 4H, H2, C 6 H 4 ), 7.57−7.54 (m, 4H, H3, 

C 6 H 4 ), 7.37−7.28 (m, 10H, Ph), 7.04 (d, 2H, H5, Im, 3 J HH = 1.8 Hz), 

6.83 (d, 2H, H4, Im, 3 J HH = 1.8 Hz), 5.48 (s, 4H, CH 2 Ph), 4.31 (t, 4H, 

CH 2 CH 2 N, 3 J HH = 6.6 Hz), 2.55 (quint, 2H, CH 2 CH 2 N, 3 J HH = 6.6 

Hz). 13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): δ 186.6 (C2, Im), 145.6 

(C1, C 6 H 4 ), 137.3 (br s, CCAu), 135.0 (C1, PhCH 2 ), 133.0 (C4, 

C 6 H 4 ), 132.6 (C3, C 6 H 4 ), 129.1 (C3, PhCH 2 ), 128.7 (C4, PhCH 2 ), 

Article 

128.2 (C2, PhCH 2 ), 123.4 (C2, C 6 H 4 ), 121.4 (C4, Im), 120.3 (C5, 

Im), 104.0 (br s, CCAu), 55.2 (PhCH 2 ), 47.4 (CH 2 CH 2 N), 31.3 

(CH 2 CH 2 N). 

L 1 Bu(AuCCPh) 2 . This was prepared in the same way as 

L 1 Bz(AuCCPh) 2 . Method A: From L 1 BuAu 2 Cl 2 (115 mg, 0.16 

mmol), Tl(acac) (101 mg, 0.33 mmol), and HCCPh (44 μL, 

0.40 mmol). Yield: 75 mg, 0.088 mmol, 55%. Method B: From 

L 1 BuAg 2 Br 2 (105 mg, 0.16 mmol) and [AuCCPh] n (98 mg, 0.33 

mmol). Yield: 93 mg, 0.11 mmol, 68%. Mp: 144 °C dec. Anal. Calcd 

for C 31 H 34 N 4 Au 2 : C, 43.47; H, 4.00; N, 6.54. Found: C, 43.55; H, 

4.24; N, 6.73. IR (KBr, cm −1 ): ν(CC) 2111. 1 H NMR (400.9 MHz, 

CDCl 3 ): δ 7.86 (d, 2H, H5, Im, 3 J HH = 2.0 Hz), 7.52−7.50 (m, 4H, 

H2, Ph), 7.28−7.18 (m, 6H, H3 and H4, Ph), 6.96 (d, 2H, H4, Im, 

3 J HH = 2.0 Hz), 6.53 (s, 2H, NCH 2 N), 4.20 (t, 4H, H1, n Bu, 3 J HH = 7.2 

Hz), 1.78 (m, 4H, H2, n Bu), 1.83 (m, 4H, H3, n Bu), 0.95 (t, 6H, Me, 

3 J HH = 7.2 Hz). 13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): δ 187.5 (C2, 

Im), 132.3 (C2, Ph), 127.9 (C3, Ph), 127.2 (CCAu), 126.6 (C4, 

Ph), 125.1 (C1, Ph), 121.6 (C4, Im), 121.0 (C5, Im), 105.5 (C 

CAu), 62.5 (NCH 2 N), 51.4 (C1, n Bu), 33.0 (C2, n Bu), 19.7 (C3, n Bu), 

13.6 (Me). 

L 1 Bu(AuCC t Bu) 2 . This was prepared in the same way as 


mmol), Tl(acac) (131 mg, 0.43 mmol), and HCC t Bu (68 μL, 


L 1 BuAg 2 Br 2 (99 mg, 0.14 mmol) and [AuCC t Bu] n (75 mg, 0.27 

mmol). Yield: 67 mg, 0.08 mmol, 59%. Mp: 114−115 °C. Anal. Calcd 



CDCl 3 ): δ 7.72 (d, 2H, H5, Im, 3 J HH = 2.0 Hz), 6.89 (d, 2H, H4, Im, 

3 J HH = 2.0 Hz), 6.50 (s, 2H, NCH 2 N), 4.1 (t, 4H, H1, n Bu, 3 J HH = 7.2 

Hz), 1.78 (m, 4H, H2, n Bu), 1.32 (m, 22H, H3, n Bu, and t Bu), 0.93 (t, 

6H, H4, n Bu, 3 J HH = 7.2 Hz). 13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): δ 

188.1 (C2, Im), 121.3 (C4, Im), 120.7 (C5, Im), 115.9 (CCAu), 

111.5 (CCAu), 62.4 (NCH 2 N), 51.2 (C1, n Bu), 33.0 (C2, n Bu), 

32.5 (CMe 3 ), 28.3 (CMe 3 ), 19.7 (C3, n Bu), 13.6 (C4, n Bu). 

L 3 Bu(AuCCPh) 2 . This was prepared in the same way as 


mmol), Tl(acac) (120 mg, 0.38 mmol), and HCCPh (52 μL, 


L 3 BuAg 2 Br 2 (94 mg, 0.14 mmol) and [AuCCPh] n (85 mg, 0.29 


for C 33 H 38 N 4 Au 2·(H 2 O) 0.7 : C, 44.18; H, 4.43, N, 6.24. Found: C, 

44.09; H, 4.49; N, 6.39. The amount of water was estimated from the 

elemental analyses and corroborated by integration of the 1 H NMR 

spectrum. IR (KBr, cm −1 ): ν(CC) 2109. 1 H NMR (400.9 MHz, 

CDCl 3 ): δ 7.50−7.48 (m, 4H, H2, Ph), 7.24−7.16 (m, 6H, H3 and 

H4, Ph), 7.12 (d, 2H, H5, Im, 3 J HH = 1.8 Hz), 6.96 (d, 2H, H4, Im, 

3 J HH = 1.8 Hz), 4.25 (t, 4H, CH 2 CH 2 N, 3 J HH = 7.1 Hz), 4.21 (t, 4H, 

H1, n Bu, 3 J HH = 7.4 Hz), 2.54 (quint, 2H, CH 2 CH 2 N, 3 J HH = 7.1 Hz), 

1.82 (m, 4H, H2, n Bu), 1.55 (s, 1.4H, H 2 O), 1.35 (m, 4H, H3, n Bu), 

0.93 (t, 6H, Me, 3 J HH = 7.4 Hz). 13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): 

δ 186.8 (C2, Im), 132.2 (C2, Ph), 128.2 (CCAu), 127.9 (C3, Ph), 

126.3 (C4, Ph), 125.7 (C1, Ph), 121.1 (C4, Im), 120.4 (C5, Im), 105.2 

(CCAu), 51.2 (C1, n Bu), 47.7 (CH 2 CH 2 N), 33.2 (C2, n Bu), 32.3 

(CH 2 CH 2 N), 19.7 (C3, n Bu), 13.7 (Me). 

L 3 Bu(AuCC t Bu) 2 . This was prepared in the same way as 



mmol). Yield: 81 mg, 0.096 mmol, 64%. Method B: From L 3 BuAg 2 Br 2 

(112 mg, 0.17 mmol) and [AuCC t Bu] n (104 mg, 0.38 mmol). Yield: 


C 29 H 46 N 4 Au 2 : C, 41.24; H, 5.49; N, 6.63. Found: C, 41.25; H, 5.88; 

N, 6.61. IR (KBr, cm −1 ): ν(CC) 2109. 1 H NMR (400.9 MHz, 


3 J HH = 2.0 Hz), 4.19 (m, 8H, CH 2 CH 2 N and H1, n Bu), 2.50 (quint, 

4H, CH 2 CH 2 N, 3 J HH = 7.2 Hz), 1.82−1.74 (m, 4H, H2, n Bu), 1.32 (s 

br, 22H, H3, n Bu, and t Bu), 0.94 (t, 6H, H4, n Bu, 3 J HH = 7.3 Hz). 

13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): δ 187.3 (C2, Im), 120.6 (C5, 

Im), 120.5 (C4, Im), 115.5 (CCAu), 112.2 (CCAu), 51.0 (C1, 

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n Bu), 47.8 (CH 2 CH 2 N), 33.1 (C2, n Bu), 32.6 (CMe 3 ), 32.5 

(CH 2 CH 2 N), 28.3 (CMe 3 ), 19.7 (C3, n Bu), 16.7 (C4, n Bu). 

L 3 Bu(AuCCC 6 H 4 NO 2 -4) 2 . This was prepared in the same way as 

L 3 Bz(AuCCC 6 H 4 NO 2 -4) 2 (method C) from L 3 BuAu 2 Cl 2 (55 mg, 

0.073 mmol), K 2 CO 3 (44 mg, 0.32 mmol), and HCCC 6 H 4 NO 2 (24 

mg, 0.16 mmol). Yield: 43 mg, 0.05 mmol, 72%. Mp: 164.7 °C dec. 

Anal. Calcd for C 33 H 36 N 6 Au 2 O 4 : C, 40.67; H, 3.72; N, 8.62. Found: C, 

40.52; H, 3.61; N, 8.60. IR (KBr, cm −1 ): ν(CC) 2105. 1 H NMR 

(400.9 MHz, CDCl 3 ): δ 8.14−8.11 (m, 4H, H2, C 6 H 4 ), 7.58−7.55 (m, 

4H, H3, C 6 H 4 ), 7.10 (d, 2H, H5, Im, 3 J HH = 2.0 Hz), 7.00 (d, 2H, H4, 

Im, 3 J HH = 2.0 Hz), 4.26 (t, 4H, CH 2 CH 2 N, 3 J HH = 6.8 Hz), 4.23 (t, 

4H, H1, n Bu, 3 J HH = 7.2 Hz), 2.53 (quint, 2H, CH 2 CH 2 N, 3 J HH = 6.8 

Hz), 1.84 (m, 4H, H2, n Bu), 1.36 (m, 4H, H3, n Bu), 0.94 (t, 6H, Me, 

3 J HH = 7.2 Hz). 13 C{ 1 H} NMR (100.8 MHz, CDCl 3 ): δ 186.2 (C2, 

Im), 145.6 (C1, C 6 H 4 ), 137.3 (br s, CCAu), 133.1 (C4, C 6 H 4 ), 

132.6 (C3, C 6 H 4 ), 123.4 (C2, C 6 H 4 ), 121.3 (C4, Im), 120.2 (C5, Im), 

103.8 (br s, CCAu), 51.3 (C1, n Bu), 47.6 (CH 2 CH 2 N), 33.1 (C2, 

n Bu), 32.0 (CH 2 CH 2 N), 19.7 (C3, n Bu), 13.6 (Me). 

L 3 Bu(AuCCSiMe 3 ) 2 . This was prepared in the same way as 

L 1 Bz(AuCCPh) 2 (method A) from L 3 BuAu 2 Cl 2 (104 mg, 0.14 

mmol), Tl(acac) (88 mg, 0.29 mmol), and HCCSiMe 3 (49 μL, 0.35 

mmol). After filtration, Et 2 O (20 mL) was added to the CH 2 Cl 2 

solution, and the resulting suspension was filtered through Celite. The 

filtrate was concentrated under vacuum to ca. 1 mL. Addition of n- 

pentane (30 mL) gave a white precipitate, which was filtered, washed 

with Et 2 O(3× 5 mL), and dried under vacuum. Yield: 53 mg, 0.060 

mmol, 43%. Mp: 156−158 °C. Anal. Calcd for C 27 H 46 N 4 Au 2 Si 2 :C, 

36.99; H, 5.29; N, 6.39. Found: C, 36.75; H, 5.63; N, 6.45. IR (KBr, 

cm −1 ): ν(CC) 2051. 1 H NMR (300.1 MHz, CDCl 3 ): δ 7.08 (d, 2H, 

H5, Im, 3 J HH = 1.9 Hz), 6.92 (d, 2H, H4, Im, 3 J HH = 1.9 Hz), 4.18 (t, 

4H, CH 2 CH 2 N, 3 J HH = 7.1 Hz), 4.16 (t, 4H, H1, n Bu, 3 J HH = 7.3 Hz), 

2.47 (quint, 2H, CH 2 CH 2 N, 3 J HH = 7.1 Hz), 1.79 (m, 4H, H2, n Bu), 

1.34 (m, 4H, H3, n Bu), 0.94 (t, 6 H, H4, n Bu, 3 J HH = 7.3 Hz), 0.21 (s, 

18H, SiMe 3 ). 13 C{ 1 H} NMR (75.5 MHz, CDCl 3 ): δ 186.8 (C2, Im), 

147.5 (CCAu), 120.7 (CH, Im), 120.6 (CH, Im), 110.4 (CCAu), 

51.1 (C1, n Bu), 47.7 (CH 2 CH 2 N), 33.2 (C2, n Bu), 32.4 (CH 2 CH 2 N), 

19.7 (C3, n Bu), 13.7 (C4, n Bu), 1.1 (SiMe 3 ). 

L 3 Bu(AuCCC 6 H 4 CF 3 -4) 2 . This was prepared in the same way as 

L 3 Bz(AuCCC 6 H 4 NO 2 -4) 2 (method C), from L 3 BuAu 2 Cl 2 (160 mg, 

0.21 mmol), K 2 CO 3 (89 mg, 0.64 mmol), and HCCC 6 H 4 CF 3 (77 

μL, 0.47 mmol). Yield: 136 mg, 0.13 mmol, 63%. Mp: 84−86 °C. Anal. 

Calcd for C 35 H 36 N 6 Au 2 F 6 : C, 41.19; H, 3.56; N, 5.49. Found: C, 


(400.9 MHz, CDCl 3 ): δ 7.57−7.55 (m, 4H, H2, C 6 H 4 ), 7.50−7.48 (m, 

4H, H3, C 6 H 4 ), 7.10 (d, 2H, H5, Im, 3 J HH = 1.8 Hz), 6.98 (d, 2H, H4, 

Im, 3 J HH = 1.8 Hz), 4.26 (t, 4H, CH 2 CH 2 N, 3 J HH = 6.9 Hz), 4.22 (t, 

4H, H1, n Bu, 3 J HH = 7.3 Hz), 2.53 (quint, 2H, CH 2 CH 2 N, 3 J HH = 6.9 

Hz), 1.83 (m, 4H, n Bu, H2), 1.35 (m, 4H, H3, n Bu), 0.94 (t, 6H, Me, 

3 J HH = 7.3 Hz). 13 C{ 1 H} NMR (75.5 MHz, CDCl 3 ): δ 186.5 (C2, Im), 

132.2 (C3, C 6 H 4 ), 129.5 (C4, C 6 H 4 ), 127.9 (q, C1, C 6 H 4 , 2 J CF = 32.3 

Hz), 124.9 (q, C2, C 6 H 4 , 3 J CF = 3.7 Hz), 124.3 (q, CF 3 , 1 J CF = 272.0 

Hz), 121.2 (C4, Im), 120.3 (C5, Im), 103.9 (CCAu), 51.2 (C1, 

n Bu), 47.6 (CH 2 CH 2 N), 33.1 (C2, n Bu), 32.1 (CH 2 CH 2 N), 19.7 (C3, 

n Bu), 13.6 (Me). 19 F NMR (282.4 MHz, CDCl 3 ): δ −62.4. 

L 3 Bu(AuCCC 6 H 4 OMe-4) 2 . This was prepared in the same way as 


0.097 mmol), K 2 CO 3 (54 mg, 0.39 mmol), and HCCC 6 H 4 OMe (32 

mg, 0.24 mmol). Yield: 82 mg, 0.087 mmol, 89%. Mp: 90−92 °C. 

Anal. Calcd for C 35 H 42 N 4 Au 2 O 2 : C, 44.50; H, 4.48; N, 5.93. Found: C, 


(400.9 MHz, CDCl 3 ): δ 7.45−7.41 (m, 4H, H3, C 6 H 4 ), 7.11 (d, 2H, 

H5, Im, 3 J HH = 1.8 Hz), 6.95 (d, 2H, H4, Im, 3 J HH = 1.8 Hz), 6.81− 

6.77 (m, 4H, H2, C 6 H 4 ), 4.25 (t, 4H, CH 2 CH 2 N, 3 J HH = 6.8 Hz), 4.20 

(t, 4H, H1, n Bu, 3 J HH = 7.3 Hz), 3.79 (s, 6H, OMe), 2.53 (quint, 2H, 

CH 2 CH 2 N, 3 J HH = 6.8 Hz), 1.81 (m, 4H, H2, n Bu), 1.34 (m, 4H, H3, 

n Bu), 0.93 (t, 6H, H4, n Bu, 3 J HH = 7.3 Hz). 13 C{ 1 H} NMR (75.5 MHz, 

CDCl 3 ): δ 186.7 (C2, Im), 158.1 (C1, C 6 H 4 ), 133.3 (C3, C 6 H 4 ), 126.2 

(br s, CCAu), 120.9 (C4, Im), 120.4 (C5, Im), 117.9 (C4, C 6 H 4 ), 

113.4 (C2, C 6 H 4 ), 104.9 (br s, CCAu), 55.1 (OMe), 51.1 (C1, 

5423 

Article 

n Bu), 47.7 (CH 2 CH 2 N), 33.1 (C2, n Bu), 32.3 (CH 2 CH 2 N), 19.7 (C3, 

n Bu), 13.6 (C4, n Bu). 

L 3 Bu(AuCCPyl) 2 . This was prepared in the same way as 


0.12 mmol), K 2 CO 3 (44 mg, 0.32 mmol), and 3-ethynylpyridine (29 

mg, 0.28 mmol). Yield: 101 mg, 0.11 mmol, 95%. Mp: 63−64 °C. 

Anal. Calcd for C 31 H 36 N 6 Au 2 : C, 42.00; H, 4.09; N, 9.48. Found: C, 


(400.9 MHz, CDCl 3 ): δ 8.72 (dd, 2H, H2, Py, 4 J HH = 2.0 and 0.8 Hz), 

8.40 (dd, 2H, H6, Py, 3 J HH = 4.8 Hz, 4 J HH = 1.6 Hz), 7.74 (dt, 2H, H4, 

Py, 3 J HH = 8.0 Hz, 4 J HH = 1.6 Hz), 7.18 (m, 2H, H5, Py), 7.11 (d, 2H, 


4H, CH 2 CH 2 N, 3 J HH = 6.9 Hz), 4.23 (t, 4H, H1, n Bu, 3 J HH = 7.3 Hz), 

2.54 (quint, 2H, CH 2 CH 2 N, 3 J HH = 6.9 Hz), 1.83 (m, 4H, H2, n Bu), 

1.35 (m, 4H, H3, n Bu), 0.94 (t, 6H, Me, 3 J HH = 7.3 Hz). 13 C{ 1 H} 

NMR (75.5 MHz, CDCl 3 ): δ 186.3 (C2, Im), 153.0 (C2, Py), 146.6 

(C6, Py), 138.8 (C4, Py), 132.7 (CCAu), 122.7 (C5, Py), 121.2 

(C4, Im), 120.3 (C5, Im), 101.5 (CCAu), 51.2 (C1, n Bu), 47.6 

(CH 2 CH 2 N), 33.1 (C2, n Bu), 32.1 (CH 2 CH 2 N), 19.7 (C3, n Bu), 13.6 

(Me); the signal of C3 of Py was not detected. 

L 3 Me(AuCCBpyl) 2 . This was prepared in the same way as 

L 3 Bz(AuCCC 6 H 4 NO 2 -4) 2 (method C), from L 3 MeAu 2 Cl 2 (104 mg, 

0.16 mmol), K 2 CO 3 (107 mg, 0.78 mmol), and HCCBpyl (66 mg, 

0.37 mmol). Yield: 120 mg, 0.12 mol, 77%. Mp: 165 °C dec. Anal. 

Calcd for C 35 H 30 N 8 Au 2·H 2 O: C, 43.13; H, 3.31; N, 11.50. Found: C, 

43.15; H, 3.03; N, 11.50. The amount of water was estimated from the 

elemental analyses and corroborated by integration of the 1 H NMR 

spectrum. IR (KBr, cm −1 ): ν(CC) 2107. 1 H NMR (400.9 MHz, 

CDCl 3 ): δ 8.77 (dd, 2H, H6, Bpyl, 4 J HH = 2.0 Hz, 5 J HH = 0.8 Hz), 8.67 

(ddd, 2H, H6′, Bpyl, 3 J HH = 4.8 Hz, 4 J HH = 1.6 Hz, 5 J HH = 0.8 Hz), 

8.36 (dt, 2H, H3, Bpyl, 3 J HH = 8.0 Hz, 4 J HH = 5 J HH = 1.2 Hz), 8.30 (dd, 

2H, H3′, Bpyl, 3 J HH = 8.4 Hz, 5 J HH = 0.8 Hz), 7.86 (dd, 2H, H4, Bpyl, 

3 J HH = 8.4 Hz, 4 J HH = 2.0 Hz), 7.80 (td, 2H, H4′, Bpyl, 3 J HH = 8.0 Hz, 

4 J HH = 1.6 Hz), 7.30−7.27 (m, 2H, H5′, Bpyl), 7.09 (d, 2H, H5, Im, 

3 J HH = 2.0 Hz), 7.01 (d, 2H, H4, Im, 3 J HH = 2.0 Hz), 4.26 (t, 4H, 

CH 2 CH 2 N, 3 J HH = 6.8 Hz), 3.96 (s, 6H, Me), 2.49 (quint, 2H, 

CH 2 CH 2 N, 3 J HH = 6.8 Hz), 1.58 (s, 2H, H 2 O). 13 C{ 1 H} NMR (75.5 

MHz, CDCl 3 ): δ 187.2 (C2, Im), 156.0 (C2′, Bpyl), 152.9 (C2, Bpyl), 

152.3 (C6, Bpyl), 149.2 (C6′, Bpyl), 139.7 (C4, Bpyl), 136.8 (C4′, 

Bpyl), 134.2 (br s, CCAu), 123.4 (C5′, Bpyl), 123.0 (C4, Im), 122.9 

(C5, Bpyl), 121.0 (C3′, Bpyl), 120.2 (C3, Bpyl), 119.7 (C5, Im), 102.0 

(br s, CCAu), 46.9 (CH 2 CH 2 N), 38.2 (Me), 31.1 (CH 2 CH 2 N). 

L 5 Me(AuCCPh) 2 . This was prepared in the same way as 

L 1 Bz(AuCCPh) 2 . Method A: From L 5 MeAu 2 Cl 2 (141 mg, 0.20 

mmol), Tl(acac) (129 mg, 0.43 mmol), and HCCPh (56 μL, 0.51 

mmol). Yield: 142 mg, 0.17 mmol, 89%. Method B: From L 5 MeAg 2 Br 2 

(82 mg, 0.15 mmol) and [AuCCPh] n (90 mg, 0.30 mmol). Yield: 66 

mg, 0.08 mmol, 53%. Mp: 92−93 °C. Anal. Calcd for C 29 H 30 N 4 Au 2 : 

42.04; H, 3.65; N, 6.76. Found: C, 41.99; H, 3.78; N, 6.87. IR (KBr, 

cm −1 ): ν(CC) 2111. 1 H NMR (300.1 MHz, CDCl 3 ): δ 7.50−7.47 

(m, 4 H, Ph), 7.26−7.19 (m, 6 H, Ph), 7.16 (d, 2H, H5, Im, 3 J HH = 1.8 

Hz), 6.83 (d, 2H, H4, Im, 3 J HH = 1.8 Hz), 4.20 (t, 4H, CH 2 CH 2 CH 2 N, 

3 J HH = 7.1 Hz), 3.85 (s, 6H, Me), 1.94 (quint, 4H, CH 2 CH 2 CH 2 N, 

3 J HH = 7.2 Hz), 1.40 (m, 2H, CH 2 CH 2 CH 2 N). 13 C{ 1 H} NMR (75.5 

MHz, CDCl 3 ): δ 187.0 (C2, Im), 132.2 (C2, Ph), 128.7 (br s, C 

CAu), 127.8 (C3, Ph), 126.3 (C4, Ph), 125.7 (C1, Ph), 122.0 (C4, 

Im), 120.7 (C5, Im), 105.3 (br s, CCAu), 50.3 (CH 2 CH 2 CH 2 N), 

38.0 (Me), 30.4 (CH 2 CH 2 CH 2 N), 22.6 (CH 2 CH 2 CH 2 N). 

L 5 Me(AuCC t Bu) 2 . This was prepared in the same way as 

L 1 Bz(AuCCPh) 2 (method A) from L 5 MeAu 2 Cl 2 (134 mg, 0.19 






3 J HH = 2.0 Hz), 4.08 (t, 4H, CH 2 CH 2 CH 2 N, 3 J HH = 6.7 Hz), 3.75 (s, 

6H, MeN), 1.78 (quint, 4H, CH 2 CH 2 CH 2 N, 3 J HH = 7.3 Hz), 1.23 (m 

and s, 20H, CH 2 CH 2 CH 2 N and t Bu). 13 C{ 1 H} NMR (100.8 MHz, 

CDCl 3 ): δ 187.6 (C2, Im), 121.9 (C4, Im), 120.6 (C5, Im), 115.4 (br 



Article 

s, CCAu), 112.7 (br s, CCAu), 50.2 (CH 2 CH 2 CH 2 N), 38.0 

(MeN), 32.6 (CMe 3 ), 30.4 (CH 2 CH 2 CH 2 N), 28.3 (CMe 3 ), 22.6 

(CH 2 CH 2 CH 2 N). 

L 5 Me(AuCCBpyl) 2 . This was prepared in the same way as 

L 3 Bz(AuCCC 6 H 4 NO 2 -4) 2 (method C), from L 5 MeAu 2 Cl 2 (77 mg, 

0.11 mmol), K 2 CO 3 (46 mg, 0.33 mmol), and HCCBpyl (49 mg, 

0.27 mmol). Yield: 103 mg, 0.10 mmol, 95%. Mp: 162 °C dec. Anal. 

Calcd for C 37 H 34 N 8 Au 2 : C, 45.13; H, 3.48; N, 11.38. Found: C, 44.80; 

H, 3.13; N, 11.18. IR (KBr, cm −1 ): ν(CC) 2111. 1 H NMR (300.1 

MHz, CDCl 3 ): δ 7.78 (dd, 2H, H6, Bpyl, 4 J HH = 2.0 Hz, 5 J HH = 0.7 

Hz), 8.67 (ddd, 2H, H6′, Bpyl, 3 J HH = 4.8 Hz, 4 J HH = 1.8 Hz, 5 J HH = 

0.9 Hz), 8.36 (dt, 2H, H3′, Bpyl, 3 J HH = 7.8 Hz, 4 J HH = 5 J HH = 1.2 Hz), 

8.29 (dd, 2H, H3, Bpyl, 3 J HH = 8.4 Hz, 5 J HH = 0.9 Hz), 7.85 (dd, 2H, 

H4, Bpyl, 3 J HH = 8.4 Hz, 4 J HH = 2.1 Hz), 7.80 (td, 2H, H4′, Bpyl, 3 J HH 

= 7.5 Hz, 4 J HH = 1.8 Hz), 7.30−7.26 (m, 2H, H5′, Bpyl), 7.14 (d, 2H, 


4H, CH 2 CH 2 CH 2 N, 3 J HH = 7.2 Hz), 3.87 (s, 6H, Me), 1.9 (quint, 4H, 

CH 2 CH 2 CH 2 N, 3 J HH = 7.2 Hz), 1.42 (m, 2H, CH 2 CH 2 CH 2 N). 

13 C{ 1 H} NMR (75.5 MHz, CDCl 3 ): δ 186.5 (C2, Im), 156.0 (C2′, 

Bpyl), 152.9 (C2, Bpyl), 152.4 (C6, Bpyl), 149.2 (C6′, Bpyl), 139.8 

(C4, Bpyl), 136.8 (C4′, Bpyl), 134.8 (br s, CCAu), 123.4 (C5′, 

Bpyl), 122.8 (C5, Bpyl), 122.1 (C4, Im), 121.0 (C3′, Bpyl), 120.7 (C5, 

Im), 120.1 (C3, Bpyl), 102.0 (br s, CCAu), 50.4 (CH 2 CH 2 CH 2 N), 

38.0 (Me), 30.4 (CH 2 CH 2 CH 2 N), 27.7 (CH 2 CH 2 CH 2 N). 

L Me AuCCSiMe 3 . To a solution of [AuCl(Im-Me 2 )] (84 mg, 0.26 

mmol) in dry CH 2 Cl 2 (10 mL) was added Tl(acac) (80 mg, 0.26 

mmol). The white suspension was stirred for 10 min and filtered 

through Celite. Then, HCCSiMe 3 (36 μL, 0.26 mmol) was added, 

and the solution was stirred for 3 h. The reaction mixture was 

concentrated under vacuum to ca. 1 mL. Addition of n-hexane (30 

mL) gave a white precipitate, which was filtered off, washed with n- 

hexane (3 × 5 mL), and dried under vacuum. Yield: 68 mg, 0.17 

mmol, 65%. Mp: 142 °C dec. Anal. Calcd for C 10 H 17 N 2 AuSi: C, 30.77; 


ν(CC) 2057. 1 H NMR (400.9 MHz, CDCl 3 ): δ 6.87 (s, 2H, CH), 

3.80 (s, 6H, Me), 0.20 (s, 9H, SiMe 3 ). 13 C{ 1 H} NMR (100.8 MHz, 

CDCl 3 ): δ 188.1 (C2, Im), 147.4 (s, CCAu), 121.8 (CH), 110.8 (s, 

CCAu), 38.0 (Me), 1.2 (SiMe 3 ). 

L Bz AuCC t Bu. To a suspension of L Bz AgBr (128 mg, 0.29 mmol) 

in CH 2 Cl 2 (12 mL) was added [AuCC t Bu] n (82 mg, 0.29 mmol). 

The gray suspension was stirred overnight at room temperature in the 

dark. It was filtered through Celite and stirred for 5 h with excess 

Na 2 S 2 O 3·5H 2 O (500 mg, 2.01 mmol). Then, it was filtered, and the 

filtrate was concentrated under vacuum to ca. 1 mL. Addition of n- 

hexane (30 mL) gave a white precipitate, which was filtered off, 

washed with n-hexane (3 × 5 mL), and dried under vacuum. Yield: 95 

mg, 0.18 mmol, 62%. Mp: 156−158 °C dec. Anal. Calcd for 

C 23 H 25 N 2 Au: C, 52,48; H, 4,79; N, 5.32. Found: C, 52.20; H, 4.76; N, 

5.42. IR (Nujol, cm −1 ): ν(CC) 2020. 1 H NMR (400.9 MHz, 

CDCl 3 ): δ 7.37−7.26 (m, 10H, Ph), 6.76 (s, 2H, H4 and H5), 5.44 (s, 

4H, CH 2 ), 1.32 (s, t Bu). 13 C{ 1 H} NMR (75.5 MHz, CDCl 3 ): δ 188.1 

(C2, Im), 135.5 (C1, Ph), 129.1 (C3, Ph), 128.7 (C4, Ph), 128.2 (C2, 

Ph), 120.8 (CH, Im), 116.0 (br s, CCAu), 111.6 (br s, CCAu), 

54.9 (CH 2 ), 32.7 (CMe 3 ), 28.5 (CMe 3 ). 

L 3 *Au 2 Cl 2 . To a solution of [AuCl(SMe 2 )] (258 mg, 0.88 mmol) 

in dry CH 2 Cl 2 (7 mL) were added tert-butylisocyanide (73 mg, 0.88 

mmol) and N,N′-diethyl-1,3-propanediamine (70 μL, 0.44 mmol). 

The solution was stirred at 60 °C for 3 days. The reaction mixture was 

filtered through Celite and concentrated under vacuum to ca. 1 mL. 

Addition of methanol (30 mL) gave a white precipitate, which was 

filtered off, washed with methanol (3 × 5 mL), and dried under 

vacuum. Yield: 230 mg, 0.30 mmol, 69%. Mp: 147 °C dec. Anal. Calcd 

for C 17 H 36 N 4 Au 2 Cl 2 : C, 26.82; H, 4.77; N, 7.36. Found: C, 26.84; H, 

4.69; N, 7.41. 1 H NMR (400.9 MHz, CDCl 3 ): δ 6.06 (s, 2H, NH t Bu), 

4.11 (t, 4H, CH 2 CH 2 N, 3 J HH = 7.2), 3.45 (q, 4H, CH 3 CH 2 N, 3 J HH = 

7.2 Hz), 1.98 (quint, 2H, CH 2 CH 2 N, 3 J HH = 7.2 Hz), 1.65 (s, 18H, 

t Bu), 1.18 (t, 6 H, CH 3 CH 2 N, 3 J HH = 7.2 Hz). 13 C{ 1 H} NMR (100.8 

MHz, CDCl 3 ): δ 190.1 (NCN), 57.1 (CH 2 CH 2 N), 54.6 (CMe 3 ), 41.3 

(CH 3 CH 2 N), 31.8 (CMe 3 ), 28.8 (CH 2 CH 2 N), 11.5 (CH 3 CH 2 N). 

5424 

[Au(CCBpyl)(CN t Bu)]. tert-Butylisocyanide (31 mg, 0.37 mmol) 

was added to a suspension of [Au(CCBpyl)] n (141 mg, 0.37 mmol) 

in CH 2 Cl 2 (10 mL). The mixture was stirred for 45 min. The solution 

was concentrated under vacuum to ca. 1 mL. Addition of Et 2 O (30 

mL) gave a beige-colored precipitate, which was filtered off, washed 

with Et 2 O(3× 5 mL), and dried under vacuum. Yield: 129 mg, 0.28 

mmol, 76%. Mp: 139−141 °C. Anal. Calcd for C 17 H 16 N 3 Au: C, 44.46; 


ν(CN) 2231, ν(CC) 2127. 1 H NMR (400.9 MHz, CDCl 3 ): δ 

8.74 (dd, 2H, H6, Bpyl, 4 J HH = 2.0 Hz, 5 J HH = 0.8 Hz), 8.66 (ddd, 2H, 

H6′, Bpyl, 3 J HH = 4.8 Hz, 4 J HH = 1.8, 5 J HH = 0.9 Hz), 8.36 (dt, 2H, H3′, 

Bpyl, 3 J HH = 8.0 Hz, 4 J HH = 5 J HH = 1.1 Hz), 8.29 (dd, 2H, H3, Bpyl, 

3 J HH = 7.4 Hz, 5 J HH = 0.84 Hz), 7.84 (dd, 2H, H4, Bpyl, 3 J HH = 8.2 Hz, 

4 J HH = 2.1 Hz), 7.80 (td, 2H, H4′, Bpyl, 3 J HH = 7.7 Hz, 4 J HH = 1.8 Hz), 

7.30−7.26 (m, 2H, H5′, Bpyl), 1.55 (s, 9H, Me). 13 C{ 1 H} NMR (75.5 

MHz, CDCl 3 ): δ 155.8, 153.4 (C2 and C2′, Bpyl), 152.6 (C6, Bpyl), 

149.1 (C6′, Bpyl), 140.1 (C4, Bpyl), 136.8 (C4′, Bpyl), 127.5 (C 

CAu), 123.5 (C5′, Bpyl), 121.8 (C5, Bpyl), 121.1 (C3′, Bpyl), 120.1 

(C3, Bpyl), 100.1 (br s, CCAu), 58.7 (CMe 3 ), 29.8 (CMe 3 ); the 

signal of AuCN was not detected. 

X-ray Crystallography. Crystals of L 3 Bu(AuCCPh) 2 and 

L 3 *Au 2 Cl 2 were obtained by liquid diffusion between a CHCl 3 

solution and Et 2 O. Both were measured on a Bruker Smart APEX 

machine at 100 K, using monochromated Mo Kα radiation (λ = 

0.71073 Å) in ω-scan mode. The structures were solved by direct 

methods and were refined anisotropically on F 2 . The nitrogen-bound 

hydrogen atoms of L 3 *Au 2 Cl 2 were refined freely with DFIX. The 

ordered methyl groups were refined using rigid groups, and the other 

hydrogen atoms were refined using a riding mode. Special features: In 

compound L 3 Bu(AuCCPh) 2 one n Bu group is disordered over two 

positions 

■ 

with a ca. 53:47% occupancy distribution. 

ASSOCIATED CONTENT 

*S Supporting Information 

Crystallographic information in CIF format, supplementary 

emission spectra, and table of crystallographic data. This 

material is available free of charge via the Internet at http:// 

pubs.acs.org. 

■ AUTHOR INFORMATION 

Corresponding Author 

*E-mail: jgr@um.es, jvs1@um.es, http://www.um.es/gqo/. 

Notes 

The authors declare no competing financial interest. 

■ ACKNOWLEDGMENTS 

We thank the Spanish Ministerio de Ciencia e Innovacioń 

(grant CTQ2007-60808/BQU, with FEDER support) and 

Fundacioń Seńeca (grant 04539/GERM/06) for financial 

support. 

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