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

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Table 5.7. Thermochemical data and bond lengths in metal carbonylsCr(CO). Mo(C0) 6 W(C0) 6 HMn 2 (C0) 10] Fe(CO), Hco2 (C0) 8 ] Ni(C0) 4.1Hj[M(CO)n·g] (kJ moi-') -908 -915 -884 -798* -725 - 593* -599D(M-CO) (kJ moi-') 107 152 180 98 118 136 147.1Hj[M. g] (kJ moi- 1 ) 397 658 860 279 416 425 430M-COterminal (av.)(Â) 1.91 2.06 2.06 1.83 1.81 1.80 1.84--*Refers to îmole.
Transition metal carbonylsbowever, tbat bond lengtbs do not provide a sensitive measure of electrondistribution witbin tbe bond, infrared spectroscopy being mucb more informative.Tbe M-C-0 system in terminal carbonyls is approximately linear; tbeangles at carbon vary from about 16 5 o -180°. In tbe gas pbase intramolecularinteractions between tbe M -C-0 unit and otber ligands may be responsible forsmall deviations from linearity. In tbe solid crystal packing forces may alsocontribute.Tbe C-0 bonds in bridging carbonyl are somewbat longer tban in terminalligands. In Fe 2 (C0) 9 (doubly bridging CO) tbe average distance is 1.176 A and inRb 6 (C0) 16 (triply bridging) 1.201 A. Tbe M-C-M angle in a symmetricalbridge is ratber acute, falling in tbe range 77-90°, compared witb about 120° ina ketone. Bridging carbonyls are less common in complexes of tbe beaviertransition elements tban in tbose oftbe First Transition Series. It bas been arguedtbat tbe bridging mode is less favoured wben tbe ligand bas to span tbe largermetal-metal distance wbicb obtains in tbe former compounds. In any case, tbeenergy differences between bridging and terminal bonding modes are ratbersmall (e.g. Co 2 (C0) 8 , p. 154). so it is difficult to predict which will occur in anyparticular case.M-C bond distances are always significantly shorter to terminal than tobridging carbonylligands. There is a general parallel between M-CO(terminal)and tbe atomic radius oftbe metal. Tbe radii oftbe corresponding elements at tbebeginning oftbe Second and Tbird Transition Series are almost equal. on accountof tbe contraction wbicb occurs across tbe lantbanides. Consequently tbe MoCO and W-CO bonds in tbe bexacarbonyls Mo(C0) 6 and W(C0) 6 are botb2.06 A in lengtb.5.2.7 Metal carbonyls-Preparation(a) DIRECT REACTION. The first binary carbonyl, Ni(C0) 4 , was reported byMond, Langer and Quincke in 1890. This volatile material is formed wben carbonmonoxide is passed over metallic nickel at or just above room temperature. Itdecomposes readily on warming. The Mond process for the extraction andrefining of nickel depends on these reactions. Crude nickel oxide mixed witboxides of iron and copper is obtained by roasting tbe sulpbide ore. Finely dividedmetal is produced by beating in bydrogen, wbicb is obtained from water gas(H 2 + CO), and tbe crude product reacted witb CO at socC/1 atm to give volatileNi(C0) 4 • This is then passed over pellets of pure nickel at 230 C when itdecomposes to metal of 99.97% purity, leaving CO to be recycled. A recentmodification of tbe process wbicb is operated in Canada employs sligbtly bigbertemperatures (130°C) and pressures (70atm) for the carbonylation. Under theseconditions a mixture of Ni(C0) 4 and Fe(C0) 5 is produced, which is separated byfractional distillation or decomposed directly to give an iron/nickel alloy. Nickelcarbonyl is very toxic and strongly carcinogenic. It is present in low concentrationsin tobacco smoke.165
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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.
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 168 and 169: co co co cooc~o o co c~co cooc~c~ o
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 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
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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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