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

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chaingrowth(alkeneinsertion)CH 3 CH2 CH=CH2"\H4NiL41l H++HNiL4ll-L+HNiL3(16)yc2H4+ +CH 3 CH2 CH 2 CH 2 NiL3 HNiL 3 (C2 H4 )1 (16) (18)C 2 H 5 ~;(C2 H 4 )L 3 )(18) "" +C2H5NiL3(16)r,_"q;c,LHNiL41l H++HNiL4ll-L ~H~ila""' j(16) ~« -~iL 3/ (18)H-L9;c, ~-~il2/ (16)(16) ~~s:: -~i(C2H4)L2 /(18)C2H#(a)(b)Fig. 12.4 Postulated catalytic cycles for (a) dimerization of ethene to 1-butene and (b) codimerization of 1. 3-butadiene and ethene to give trans-1, 4-hexadiene.
Catalysis of reactions of alkenes by transition metal complexesbutene or add a second ethane molecule leading to chain growth. The relativeimportance of these two paths can be controlled by changing the phosphineligands. In the system [ (17 3 -C 3 H 5 )NiCl],/EtAlC1 2 /L at - 20°C/ 1 atm. for instance,only 1-butene is formed when L = Me 3 P. Bulky phosphines hinder /3-hydrogentransfer more than alkene insertion. When L = P( cyclohexyl) 3 , 70% bute ne, 2 5%hexene and 5% higher oligomers are formed. In the extreme case of L = PBu~.olefin elimination is essentially repressed, so that polyethene is produced.Selective codimerization of ethene and 1, 3-butadiene is also possible becausethe diene first forms an 17 3 -allyl complex with the metal centre (Fig. 12.4). Anindustrial process along these lines has been developed in the USA by Du Pont.A rhodium catalyst is employed; rhodium trichloride in ethanol itself gives 80%selectivity towards the desired product, trans-1, 4-hexadiene, which is used in themanufacture of an ethene-propene-hexadiene synthetic rubber. The dieneintroduces some double bonds into the polymer chains which are required forvulcanization.12.3.5 Oligomerization of butadieneWilke and his coworkers at the Max Planck Institut fiir Kohlenforschung atMiilheim, Ruhr, ha ve extensively studied oligomerization reactions of butadieneusing a wide range of transition metal catalysts. Those based on nickel and onpalladium are the most useful. Nickel systems generally afford cyclic products,whereas linear materials are obtained using palladium.The nickel catalyst is obtained by reduction of a nickel(II) compound such asthe acetylacetonate in the presence of butadiene, or simply by exchange ofbutadiene and bis(17 3 -allyl)nickel or bis(cycloocta-1. 5-diene)nickel. In the absenceof added ligands, butadiene is rapidly and catalytically converted at lowtemperatures into 1, 5, 9-cyclododecatriene, mainly the trans, trans. trans isomer.The trimerization bears the mark of a 'template' process, three butadienemolecules linking very specifically around a 'naked nickel' centre. Detailedstudies show that the process is not synchronous but occurs in a stepwise fashion(Fig. 12.5 ).The C 12 1J 2 • 17 3 • 17 3 -intermediate has been isolated from the reaction mixture at- 40°C. The 1 H n.m.r. spectrum shows that in solution two isomers are present inwhich the allyl groups bear anti substituents. With PMe 3 an adduct is formed inwhich isomerization to syn substituents has occurred, presumably via an 17 1 -intermediate. This isomerization explains why the trans, trans. trans isomer ofcyclododecatriene is the major product. Cyclododecatriene is used as a precursorto Nylon 12.When a tertiary phosphine or phosphite L is added in the ratio l: 1 (Ni:L),coordination of a third butadiene molecule is prevented, so that dimers ratherthan trimers result. The first key intermediate is an 17 1 ,17 3 -octadienyl complex.This gives rise to vinylcyclohexene (VCH). If Lis weakly basic. X rearranges to an17 3 , 17 3 -C 8 H 12 species Y which leads to cis-1. 5-cyclooctadiene (COD) (Fig. 12.6).367
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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
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
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 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 392 and 393: Me3 CCH2Li3HCI/WCL 6 W(=CBut)(CH2 B
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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