_P.-Powell-auth.-Principles-of-Organometallic-Chemistry-Springer-Netherlands-1988

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Five electron ligandsa pair of non-bonding electrons. (In the 16-electron compound Cp 2 TiCl 2 theequivalent orbital is vacant.) Cp 2 MoH 2 acts as a base, being protonated bytrifluoroacetic acid to give Cp 2 MoH; and forming adducts Cp 2 MoH 2 .BF 3 andCp 2 MoH2'AlMe 3 with Lewis acids. The tungsten complex is similar.Mean bond dissociation energies D(M-H) and D(M-Me) in the compoundsCp 2 MX 2 are as follows: D(M-H)/kJmol- 1 : Mo, 252; W, 305. D(M-Me): Mo,159; W, 209. Consider the hypothetical addition of methane to Cp 2 M:Cp 2 M + H-Me~Cp 2 M(H)Mein which a C-H bond is broken and M-H and M-Me bonds are formed. Giventhat D(C-H) in methane is 435kJmol-1, AHreaction is +24kJmol- 1 (M=Mo)and -79 kJmol- 1 (M = W). TASB-is estimated tobe about 55 kJmol- 1 at 298Kowing to the loss of one mole of gaseous methane. Although this reaction has notbeen observed in this system with methane, other hydrocarbons have beenshown to react with Cp 2 WH 2 when they are irradiated with ultraviolet light.It is believed that the addition proceeds through a labile tungstenocene species'Cp 2 W'. Spectroscopic investigations of the species produced on photolysis ofCp 2 WH 2 in an argon matrix at 20 K are consistent with this interpretation. Cp 2 Wapparently has a triplet ground state like chromocene, but is much more reactivebehaving more like a diradical. This radical character is shared by other biscyclopentadienyls of the heavy transition elements (apart from Ru, Os). Wherethey have been observed at ali the monomers are very short lived and dimerizerapidly to products rather complicated structures.9.3 Cyclopentadienylmetal carbonylsThe cyclopentadienyl metal carbonyls form a large group of compounds thechemistry of which has been explored in detail. Consequently only a few generalfeatures can be covered here. Most ofthese compounds obey the 18-electron rule.This is clearly illustrated by the series of mononuclear complexes CpV(C0) 4 ,CpMn(C0) 3 and CpCo(C0) 2 (Fig. 9.9). The simplest derivatives ofthe interveningelements Cr, Pe and Ni are binuclear; here the electron count is attained bymetal-metal bonding or by electron sharing through bridging carbonyls. Theformation of binuclear systems by alternate members of the transition seriesresembles the similar formation of binuclear carbonyls in the series Cr(C0) 6 ,Mn 2 (C0) 10 , Fe(C0) 5 , Co 2 (C0) 8 and Ni(C0) 4 •292
MONONUCLEAR~ ~ ~Vcd\c'co oo o,.Mnc/1 "'-o c co oANIONS CpV(CO)~- CpFe(C0) 2 -Coc/"'-co oCpCr(C0)3 -e jf +e-e Jf +e@< c co @_ o 82.5 co,, .. -c~, '-.../ //-'l. /SI NUCLEAR o3.2 e1 L-~co·"'"""Jr c- @J"'-Coc c ooo~ Fe/Fe~~~ ~c o ~Fig. 9. 9 Structures of some cyclopentadienyl carbonyl complexes.~Ni1NoCpNi(CO)--e j[ +eoc,,~~.. ~o([1;"',. ~\~ =. \\"' -.2.363 N''W
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Principles ofOrganometallicChemistr
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© 1988 P. PowellOriginally publish
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Contentsvi3.5 Beryllium 543.6 Calci
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Contents12.4 Chemistry based on syn
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PrefaceIn the 20 years since 'Princ
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Periodic table ofthe elementsThe pe
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Periodic table of elementsGroup Gro
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General surveysyntheses. They are a
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General surveypacked hexagonal, nic
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Table 1.1. Mean metal-carbon bond d
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General survey(c) COMPLEXES OF UNSA
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General survey4008.0o1E...,300.=; 2
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General surveyelements are rapidly
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General surveyCollman, J.P., Hegedu
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100o-100o Si110111Ql-200 . 1L. :1o
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The main group elementsFor R = alky
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The main group elementsweakly exoth
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The main group elementselement and
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The main group elements(a) HYDROSIL
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The main group elementsinsertion:-
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The rnain group elernentsElectrophi
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The first three periodic groupsTabl
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The first three periodic groupstran
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The first three periodic groups(o)(
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The first three periodic groups( b)
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The first three periodic groupsorga
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The first three periodic groupsMe M
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The first three periodic groupsH HE
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The first three periodic groupsThis
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The first three periodic groupsHere
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The first three periodic groupselec
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The first three periodic groupsEt~5
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The first three periodic groupscond
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The first three periodic groupsThe
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1 2·65 1 9-...:..... _;.;;.-c 1·4
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The first three periodic groupsCycl
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The first three periodic groups3. 7
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The first three periodic groupsYe\
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The first three periodic groupsor o
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Table 3.6 Some hydroborating agents
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RCf:0~HH~RCHO2 2Hi~OH-"' 18-C-R/ 1o
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The first three periodic groups(c)
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The first three periodic groupsTHF.
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The first three periodic groupspuls
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The first three periodic groupsROH/
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The first three periodic groupsthe
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The first three periodic groupsThe
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The first three periodic groupsin p
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The first three periodic groupsSilv
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The first three periodic groupso-RR
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The first three periodic groups(a)(
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The first three periodic groups5. W
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4Organometallic compoundsof element
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The main Groups IV and Vachieved e.
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The main Groups IV and Ve.g. alipha
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The main Groups IV and VDimethyltin
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The main Groups IV and V4.3.3 React
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The main Groups IV and Villustrates
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The main Groups IV and Vof methylco
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The main Groups IV and VTable 4.1.
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The main Groups IV and Vanes) are s
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The main Groups IV and Vconcentrati
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The main Groups IV and VTable 4.2.
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The main Groups IV and V4.6.3 Caten
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The main Groups IV and VTreatment o
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The main Groups IV and V4.8 pTC-JJT
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The main Groups IV and VA convenien
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The main Groups IV and Vfu- +( + )[
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The main Groups IV and Vand Me 2 PF
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The main Groups IV and VAcidH 2 PO(
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The main Groups IV and Vin World Wa
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The main Groups IV and VHX(SblPh M
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The main Groups IV and VOn replacem
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The main Groups IV and Varsenic yli
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The main Groups IV and VPh 2 BiBiPh
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The main Groups IV and Vphosphorus
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The main Groups IV and VDimethyltin
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5Some transition metalchemistry rel
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M L--4----f/~1 11 1\ 11 11 1\ 11 11
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Transition metal chemistryeven nega
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co co co cooc~o o co c~co cooc~c~ o
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Transition metal chemistryeach othe
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Transition metal chemistryconsidere
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Transition metal chemistryTable 5.3
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Transition metal chemistryTable 5.5
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Table 5.7. Thermochemical data and
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Transition metal chemistryNickel is
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Transition metal chemistry(o)(OC ln
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Transition metal chemistryCarbonyl
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Transition metal chemistry2Cr(COJ6
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Transition metal chemistry18-electr
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Table 5.8. General reactions of tra
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Transition metal chemistry5. 3.1 Ad
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Transition metal chemistrynot detec
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Transition metal chemistryPd(PPhBu~
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Transition metal chemistryH2 -LL3Rh
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Transition metal chemistryPhosphine
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Transition metal chemistry(d) Comme
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Transition metal chemistryD: 1 Hn.m
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Organometallic compounds of the tra
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No3-electron1] 3 -allyl4-electron17
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Organotransition metal chemistrymel
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Organotransition metal chemistryii)
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Table 7.2. Mechanisms of decomposit
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Organotransition metal chemistry4Ti
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Organotransition metal chemistryM e
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Organotransition metal chemistryIn
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Organotransition metal chemistryThe
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Organotransition metal chemistry~ (
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Organotransition metal chemistryo o
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Organotransition metal chemistry( C
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Organotransition metal chemistryMe
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Organotransition metal chemistry/OM
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Organotransition metal chemistry7.3
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Organotransition metal chemistryexc
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Page 260 and 261: Organotransition metal chemistryR R
Page 262 and 263: Organotransition metal chemistry-co
Page 264 and 265: Organotransition metal chemistry4.
Page 266 and 267: Organotransition metal chemistry(b)
Page 268 and 269: r~...I.J::...--Î-..L-.._.,:;.I""'
Page 270 and 271: Allyl and diene complexessignals ar
Page 272 and 273: Allyl and diene complexesdoublets.
Page 274 and 275: Allyl and diene complexes111.5°. A
Page 276 and 277: Allyl and diene complexesThe pallad
Page 278 and 279: Allyl and diene complexesFe(C0} 5-F
Page 280 and 281: Allyl and diene complexes~4,neutrat
Page 282 and 283: Allyl and diene complexesThis indic
Page 284 and 285: Allyl and diene complexesonly with
Page 286 and 287: Allyl and diene complexesderivative
Page 288 and 289: Allyl and diene complexesvolatile,l
Page 290 and 291: Allyl and diene complexesChemical R
Page 292 and 293: 9Five electron ligands9.1 lntroduct
Page 294 and 295: Five electron ligandsTable 9.1 The
Page 296 and 297: Five electron ligandsthe ferriceniu
Page 298 and 299: Five electron ligandsFerrocene unde
Page 300 and 301: Five electron ligands---v~···Fe,
Page 302 and 303: Five electron ligandsDihalogenometh
Page 304 and 305: Five electron ligands(c) TITANOCENE
Page 308 and 309: Five electron ligands9. 3.1 Mononuc
Page 310 and 311: Five electron ligandsslowly oxidize
Page 312 and 313: ~ o coo,... ...,C,, /....-:;.' //Fe
Page 314 and 315: Five electron ligandsn-system of ea
Page 316 and 317: Five electron ligandsFig. 9.15 Mole
Page 318 and 319: Five electron ligandsNucleophilic r
Page 320 and 321: Five electron ligands(a) Sketch the
Page 322 and 323: lCH2=CHC2H5Five electron ligands(i)
Page 324 and 325: Five electron ligands( 6 A 1 g) and
Page 326 and 327: Complexes of arenesFor chromium thi
Page 328 and 329: Complexes of arenesW(C 6 H 6 ) 2
Page 330 and 331: Complexes of arenesgas phase (5.01
Page 332 and 333: Complexes of arenes(Q)-RCr cr(C0)
Page 334 and 335: Complexes of arenes- BH 3~jCr(C0) 3
Page 336 and 337: Complexes of arenesif"••d•R"x
Page 338 and 339: wNfoi::>.~7trienyl Cr(C0) 3~·trien
Page 340 and 341: Complexes of arenesmethyl iodide. T
Page 342 and 343: Complexes of arenesin the whole mol
Page 344 and 345: Complexes of arenesproposed above,
Page 346 and 347: Complexes of arenesProblems1. Ferro
Page 348 and 349: Complexes of arenes(<) ~PlMe~MeMe~M
Page 350 and 351: Table 11.1. Electron counting in cl
Page 352 and 353: Cluster compounds455TrigonalOctahed
Page 354 and 355: Cluster compoundsFig. 11.4 Closo, a
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Cluster compoundsmixture of the mor
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Cluster compoundsIt is extremely st
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Cluster compounds2- 2-~ m1 11O GQ8-
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Cluster compounds(IJ 5 -C,B,H 6 )Mn
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wUlo2-Fe(C0) 5redu cine;~C 7 H~BF4-
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Cluster compoundsdensations' do not
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Cluster compoundsA 3 A 78 78 12A 3c
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Cluster compoundsstructures of the
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Mechanisms of industrial processesT
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Table 12.2.Process Feedstock Cataly
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Mechanisms of industrial processesF
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Mechanisms of industrial processes1
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chaingrowth(alkeneinsertion)CH 3 CH
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r!~~NiJy ~ ' ,. -;,,.,~,;, ..'Ni'+2
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ţ/Ph)o-cPd =:) )cH0-C'-....Ph 2~-8
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Mechanisms of industrial processesH
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H2 C=CH2H2C=CH2[Ti]-R + C2H4coordin
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o[~] o ~ [f!- ~7:Jlinear[w]=CH~poly
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Me3 CCH2Li3HCI/WCL 6 W(=CBut)(CH2 B
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Mechanisms of industrial processesW
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Mechanisms of industrial processesT
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••~'"'"'" 7 ~;~13 :H~ r--------
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Mechanisms of industrial processesc
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Mechanisms of industrial processesO
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Mechanisms of industrial processesc
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Mechanisms of industrial processesH
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a)oIIIc1c1o1H /H'-cH2 ,l!--1 --H'.
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Mechanisms of industrial processesB
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Mechanisms of industrial processes5
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Lanthanides and actinidesA few exam
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Lanthanides and actinidesCp~LuCH 3
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IndexOrganometallic compounds are i
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IndexCarbon monoxide contd.bonding
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IndexEthylene glycol. see Ethane-1.
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IndexMetallocenes contd.reactions,
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IndexSilicon contd.-silicon bonded
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_P.-Powell-auth.-Principles-of-Organometallic-Chemistry-Springer-Netherlands-1988

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