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

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Five electron ligandsFerrocene undergoes the Vilsmeier reaction with PhNMeCHO /POCl 3 to yieldferrocenal, FcCHO, a reagent which is useful in the synthesis of numerousderivatives. With formaldehyde and secondary amines (Mannich condensation)the monodialkylamino derivative FcCH 2 NR 2 is produced. These reactions do notoccur with benzene itselfbut only with very reactive compounds such as phenol.Electrophilic mercuration of ferrocene by mercury(II) acetate to give FcHg(OAc)occurs at a rate 10 9 times that of the corresponding reaction with benzene. It ispossible that the initial step involves an intermediate with an iron-mercurybond. A blue adduct Cp 2 Fe · 2HgCl 2 has been isolated; the structure of a similarBr Brruthenium compound Cp 2 Ru-Hg(,u-Br) 2 Hg-RuCp 2 has been determined byX-ray diffraction.~CH 2 NMo 2 Me 2 NHFeCpCH 2 0MANNICH~PhNMeCHOFeCpPOCL 3VILSMEIER~CHO CH 2 (C0 2 Hl 2FeCpba seKNOEVENAGEL~CH~CHC0 2 HFeCpSulphonation can be achieved with sulphuric acid or, better, with chlorosulphonicacid, ClS0 3 H, in acetic anhydride.Friedel-Crafts alkylation of ferrocene often leads to polysubstitution and isaccompanied by side reactions, including oxidation to Cp 2 Fe + which is inert toelectrophiles. The reactions with aryldiazonium salts are thought to involve arylradicalsas the ferricinium ion is inert to ArN; .(e) METALLATION. Ferrocene can readily be metallated. This metallationresembles the hydrogen-exchange reactions typical of aromatic hydrocarbons(p. 40). n-Butyllithium yields mainly lithioferrocene and 1, 1'-dilithioferrocenecan be obtained using the BunLi. TMEDA complex. These lithiated derivatives areprecursors to a wide range of substituted compounds, some of which, such ashalogeno- or nitroferrocene, cannot be obtained by direct electrophilic attack onthe parent. Some examples are shown in Fig. 9.4.284
Bis(cyclopentadieny l )complexesfrPPh2~Fe (Bidentote~Ugood)PPhzFeCpFeCpl··""Li BulTMEDA~Fe@LiBu--·(I)C0 2(ii)H+~uFe@/(i)HCHO(ii)H+(il R 2 CO(iilH+~C(OH)R 2~FeCp1FeCpreduction~B(OH) 2~SIR 3~NH 21FeCp1HgCL2-~HgCI Br 2FeCpFeCp~iCLMgFt!Cp~"' - ~"'"'Fe FeCp CpFig. 9.4 Some reactions of ferrocenyllithium.(f) STABILIZA TION OF et-CARBONI UM IONS. A feature of ferrocene chemistry isthe ready stabilization of a carbonium ion in which the positive charge isconcentrated a- to one ring. Crystalline salts can be isolated from the protonationof ferrocenyl carbinols or vinylferrocenes with acids such as HPF 6 , which ha veweakly coordinating anions.285
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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
Page 248 and 249: Organotransition metal chemistryMe
Page 250 and 251: Organotransition metal chemistry/OM
Page 252 and 253: Organotransition metal chemistry7.3
Page 254 and 255: Organotransition metal chemistryexc
Page 256 and 257: Organotransition metal chemistrysev
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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 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 306 and 307: Five electron ligandsa pair of non-
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
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Complexes of arenes(<) ~PlMe~MeMe~M
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Table 11.1. Electron counting in cl
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Cluster compounds455TrigonalOctahed
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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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