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

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co co co cooc~o o co c~co cooc~c~ o coOC CO Fe Fe OC Co Co CO Co Cooc co 5 co co co oc co cococo co co co coM T R (D ) Fe 2 (C0) 9 (D 7 h) Co2(C0)8 two isomers (D3d,C2v)M2(C0)10 ,M= n, c, e 4d "coco\ cooc, 1 ~.J,.d-co/Fe~Jr.oc 11/~~coco cooc coco co oc 1/"~---IÎI-co/1 """"-Mcoco co /l"coco coMe 3 (C0)12, M = Ru,Os(D 3h)coq c,.ocloRhs(C0)16(T d )Fig. 5.4 Structures of some bi- and polynuclear carbonyl complexes.
Transition metal carbonylshas been prepared from the reaction between [V(CO),p- and Ph,AuCl in THF.Cocondensation ofvanadium vapour with carbon monoxide in a frozen matrix ofnoble gas affords V(C0) 6 and probably also the dimer. The metal-metal bondenergies decrease from 88kJmol-' in Co 2 (C0) 8 to 75kJmol-' in Mn 2 (C0) 10 •Extrapolation to vanadium would indicate an extremely weak bond in the dimerV 2 (C0), 2 • The molecular structures of some bi- and polynuclear carbonyls areshown in Fig. 5 .4. Further examples are given in Chapter 11. These reveal someof the varied modes of bonding which the carbonyl ligand can adopt.In general carbon monoxide can be considered to be a two electron donor as faras electron counting is concerned (see p. 191 ). It can act as a terminalligand orasa bridge between two (,U 2 -CO) or three (,u 3 -CO) metal atoms. In nearly ali knownexamples of bridge formation, the metal atoms are within bonding distance ofIlle\o oCO os aIII2- electron cdonor1MM--MTerminal Doubly Semi-bridgingbridging(symmelricol)TripLy bridgingExempleFe 2(COJ91/;0co as o/\4- electron M--MdonorTT-CO (donation fromone TT -syslem)[cpMo(C0/2]2 (p. 300JTripLy bridgingrr- CO(donolion fromone rr-system)Examp~eMn 2 (CO) 6 dppmCO as a6-electrondonorDan alian from bothTT- syslemsExemple.[ Cp Nb(C0) 2 ] 3155Fig. 5.5 Modes of bonding of the carbonyl!igand.
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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
Page 118 and 119: The main Groups IV and VDimethyltin
Page 120 and 121: The main Groups IV and V4.3.3 React
Page 122 and 123: The main Groups IV and Villustrates
Page 124 and 125: The main Groups IV and Vof methylco
Page 126 and 127: The main Groups IV and VTable 4.1.
Page 128 and 129: The main Groups IV and Vanes) are s
Page 130 and 131: The main Groups IV and Vconcentrati
Page 132 and 133: The main Groups IV and VTable 4.2.
Page 134 and 135: The main Groups IV and V4.6.3 Caten
Page 136 and 137: The main Groups IV and VTreatment o
Page 138 and 139: The main Groups IV and V4.8 pTC-JJT
Page 140 and 141: The main Groups IV and VA convenien
Page 142 and 143: The main Groups IV and Vfu- +( + )[
Page 144 and 145: The main Groups IV and Vand Me 2 PF
Page 146 and 147: The main Groups IV and VAcidH 2 PO(
Page 148 and 149: The main Groups IV and Vin World Wa
Page 150 and 151: The main Groups IV and VHX(SblPh M
Page 152 and 153: The main Groups IV and VOn replacem
Page 154 and 155: The main Groups IV and Varsenic yli
Page 156 and 157: The main Groups IV and VPh 2 BiBiPh
Page 158 and 159: The main Groups IV and Vphosphorus
Page 160 and 161: The main Groups IV and VDimethyltin
Page 162 and 163: 5Some transition metalchemistry rel
Page 164 and 165: M L--4----f/~1 11 1\ 11 11 1\ 11 11
Page 166 and 167: Transition metal chemistryeven nega
Page 170 and 171: Transition metal chemistryeach othe
Page 172 and 173: Transition metal chemistryconsidere
Page 174 and 175: Transition metal chemistryTable 5.3
Page 176 and 177: Transition metal chemistryTable 5.5
Page 178 and 179: Table 5.7. Thermochemical data and
Page 180 and 181: Transition metal chemistryNickel is
Page 182 and 183: Transition metal chemistry(o)(OC ln
Page 184 and 185: Transition metal chemistryCarbonyl
Page 186 and 187: Transition metal chemistry2Cr(COJ6
Page 188 and 189: Transition metal chemistry18-electr
Page 190 and 191: Table 5.8. General reactions of tra
Page 192 and 193: Transition metal chemistry5. 3.1 Ad
Page 194 and 195: Transition metal chemistrynot detec
Page 196 and 197: Transition metal chemistryPd(PPhBu~
Page 198 and 199: Transition metal chemistryH2 -LL3Rh
Page 200 and 201: Transition metal chemistryPhosphine
Page 202 and 203: Transition metal chemistry(d) Comme
Page 204 and 205: Transition metal chemistryD: 1 Hn.m
Page 206 and 207: Organometallic compounds of the tra
Page 214 and 215: No3-electron1] 3 -allyl4-electron17
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Organometallic compounds of the tra
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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
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Complexes of arenesin the whole mol
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Complexes of arenesproposed above,
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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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