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

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Me3 CCH2Li3HCI/WCL 6 W(=CBut)(CH2 But) 3dme• W(=CBut)(dme)Cl3H2 0/Me3 PEt3 NH OButc~ll / PMe3~w-·~,,Me3 P CLCLH2C=CHMeBut[wJ'_.,...cH"--"-. /CH2cw"'MeBut/CH"-....+ [w] /CHMe'-.....cH2-sutCH=CH [W]=CHMe + [W)=CH2(R=H,Me)-But= -CMe3 ; dme= 172-dimethoxyethone ; [w] = W(O)(PMe 3 ) 2 Ct 2 .Fig. 12.12 Preparation of an oxo-tungsten complex, an active catalyst for metathesis of alkenes.
Catalysis of reactions of alkenes by transition metal complexesA related tungsten complex (R'0) 2 W(=NR)(=CHBut) is an exceptionallyactive catalyst for alkene metathesis. Its activity is unchanged over periods of atleast 1 day and the turnover is in hundreds of conversions per minute. A trigonalbipyramidal tungstenacyclobutane intermediate is again involved.',','R'O OR'Some alkene metathesis catalysts, notably WCl 6 activated by Me 4 Sn, aretolerant ofmany functional groups such as -C0 2 R, -COR, -CN, -halogen or-OSiMe 3 • Fischer carbenes such as Ph(MeO)C= W( C0) 5 in the presence ofLewisacids are also useful. This has been exploited in the synthesis of long chaindicarboxylic esters from, for example, methyl oleate.CH,(CH 2 ),CH=CH(CH 2 ),C0 2 Me CH,(CH 2 ) 7 CH=CH(CH 2 ) 7 CH,IlO C+ Me0 2 C(CH 2 ),CH=CH(CH 2 ) 7 C0 2 MeDicarboxylic esters are used to prepare polyesters and polyamides. The residualdouble bonds permit cross-linking of the polymer chains. Cross metathesis ofmethyl oleate with excess ethene affords methyl 9-decenoate, a key intermediatein the synthesis of 'queen bee substance', a honey bee pheromone.CH,(CH 2 ) 7CH=CH(CH 2 ),C0 2 Me~H 2 C=CH(CH 2 ) 7 CH,+H 2 C=CH 2 H 2 C=CH(CH 2 ),C0 2 Me--->+---> MeCO(CH 2 ),CH=CHC0 2 MeThe compositions of classical Ziegler-Natta and metathesis catalysts are verysimilar. It has therefore been suggested by Green and also by Schrock that ZieglerNatta polymerization might occur via alkylidene intermediates. The tantalumcomplex Ta(CHCMe,)H(PMe 3 ) 3I 2 , for example, in toluene converts ethene into aliving polymer.H H1 1 a-H transferM-C-R1 1CH2 CH 2tretc.379
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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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Organotransition metal chemistrysev
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Organotransition metal chemistry)--
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Organotransition metal chemistryR R
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Organotransition metal chemistry-co
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Organotransition metal chemistry4.
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Organotransition metal chemistry(b)
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r~...I.J::...--Î-..L-.._.,:;.I""'
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Allyl and diene complexessignals ar
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Allyl and diene complexesdoublets.
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Allyl and diene complexes111.5°. A
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Allyl and diene complexesThe pallad
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Allyl and diene complexesFe(C0} 5-F
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Allyl and diene complexes~4,neutrat
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Allyl and diene complexesThis indic
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Allyl and diene complexesonly with
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Allyl and diene complexesderivative
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Allyl and diene complexesvolatile,l
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Allyl and diene complexesChemical R
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9Five electron ligands9.1 lntroduct
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Five electron ligandsTable 9.1 The
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Five electron ligandsthe ferriceniu
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Five electron ligandsFerrocene unde
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Five electron ligands---v~···Fe,
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Five electron ligandsDihalogenometh
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Five electron ligands(c) TITANOCENE
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Five electron ligandsa pair of non-
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Five electron ligands9. 3.1 Mononuc
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Five electron ligandsslowly oxidize
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~ o coo,... ...,C,, /....-:;.' //Fe
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Five electron ligandsn-system of ea
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Five electron ligandsFig. 9.15 Mole
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Five electron ligandsNucleophilic r
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Five electron ligands(a) Sketch the
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lCH2=CHC2H5Five electron ligands(i)
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Five electron ligands( 6 A 1 g) and
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Complexes of arenesFor chromium thi
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Complexes of arenesW(C 6 H 6 ) 2
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Complexes of arenesgas phase (5.01
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Complexes of arenes(Q)-RCr cr(C0)
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Complexes of arenes- BH 3~jCr(C0) 3
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Complexes of arenesif"••d•R"x
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wNfoi::>.~7trienyl Cr(C0) 3~·trien
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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
Page 356 and 357: Cluster compoundsmixture of the mor
Page 358 and 359: Cluster compoundsIt is extremely st
Page 360 and 361: Cluster compounds2- 2-~ m1 11O GQ8-
Page 362 and 363: Cluster compounds(IJ 5 -C,B,H 6 )Mn
Page 364 and 365: wUlo2-Fe(C0) 5redu cine;~C 7 H~BF4-
Page 366 and 367: Cluster compoundsdensations' do not
Page 368 and 369: Cluster compoundsA 3 A 78 78 12A 3c
Page 370 and 371: Cluster compoundsstructures of the
Page 372 and 373: Mechanisms of industrial processesT
Page 374 and 375: Table 12.2.Process Feedstock Cataly
Page 376 and 377: Mechanisms of industrial processesF
Page 378 and 379: Mechanisms of industrial processes1
Page 380 and 381: chaingrowth(alkeneinsertion)CH 3 CH
Page 382 and 383: r!~~NiJy ~ ' ,. -;,,.,~,;, ..'Ni'+2
Page 384 and 385: ţ/Ph)o-cPd =:) )cH0-C'-....Ph 2~-8
Page 386 and 387: Mechanisms of industrial processesH
Page 388 and 389: H2 C=CH2H2C=CH2[Ti]-R + C2H4coordin
Page 390 and 391: o[~] o ~ [f!- ~7:Jlinear[w]=CH~poly
Page 394 and 395: Mechanisms of industrial processesW
Page 396 and 397: Mechanisms of industrial processesT
Page 398 and 399: ••~'"'"'" 7 ~;~13 :H~ r--------
Page 400 and 401: Mechanisms of industrial processesc
Page 402 and 403: Mechanisms of industrial processesO
Page 404 and 405: Mechanisms of industrial processesc
Page 406 and 407: Mechanisms of industrial processesH
Page 408 and 409: a)oIIIc1c1o1H /H'-cH2 ,l!--1 --H'.
Page 410 and 411: Mechanisms of industrial processesB
Page 412 and 413: Mechanisms of industrial processes5
Page 414 and 415: Lanthanides and actinidesA few exam
Page 416 and 417: Lanthanides and actinidesCp~LuCH 3
Page 418 and 419: IndexOrganometallic compounds are i
Page 420 and 421: IndexCarbon monoxide contd.bonding
Page 422 and 423: IndexEthylene glycol. see Ethane-1.
Page 424 and 425: IndexMetallocenes contd.reactions,
Page 426 and 427: IndexSilicon contd.-silicon bonded
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_P.-Powell-auth.-Principles-of-Organometallic-Chemistry-Springer-Netherlands-1988

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