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

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Organotransition metal chemistry(b) Discuss each of the reaction steps.( c) Predict the composition of any gaseous products formed when F is heated,explaining the mechanism of the reactions involved.(University of Southampton).252
8Allyl and dienecomplexes of thetransition elements8.1 Allyl (-enyl) complexesThere are two main ways in which the allyl group can link to a transitionelement. Either it is attached through one of the terminal carbon atoms (IJ 1 )leaving an uncoordinated double bond, or all three carbon atoms of the allylsystem are bounded (1J 3 ).~ 1 -allyl8.1.1 N.m.r. and dynamic processesA useful way of distinguishing between these bonding modes is by proton n.m.r.spectroscopy. The spectra of one IJ 1 - and one IJ 3 - complex are given in Fig. 8.1.Consider the spectrum of 1J 1 -C 3 H 5 Mn(C0) 5 first. The H 1 (W') protons arerelatively strongly shielded by the adjacent metal atom. They therefore resonateat high field, 1.8 13. If H 1 and H 1 ' are magnetically equivalent, that is related inspace by a symmetry operation on the molecule, this resonance is a doublet ofrelative intensity 2, 3 H(H 1 H 2 )"' 8 Hz.*The remaining protons H 2 , H 3 , H 4 are substituents on a vinyl (alkenyl) group.Such resonances appear typically at 4.5-613 in alkenes. The trans vicinalcoupling constant 'J(H 2 H 3 ) is greater than the cis vicinal constant 'J(H 2 H 4 ). The*Ifthe two protons are not so related they are magnetically inequivalent or 'enantiotopic'and two separate signals with different chemical shift values will appear. In this casegeminaL coupling 2 ](H'H 1 '). the magnitude of which is related to the angle H 1 CH 1 ', isobserved as well as vicinal coupling 3 J(H 1 H 2 ), 3 J{H 1 'H 2 ).253
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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
Page 216 and 217: Organometallic compounds of the tra
Page 228 and 229: Organotransition metal chemistrymel
Page 230 and 231: Organotransition metal chemistryii)
Page 232 and 233: Table 7.2. Mechanisms of decomposit
Page 234 and 235: Organotransition metal chemistry4Ti
Page 236 and 237: Organotransition metal chemistryM e
Page 238 and 239: Organotransition metal chemistryIn
Page 240 and 241: Organotransition metal chemistryThe
Page 242 and 243: Organotransition metal chemistry~ (
Page 244 and 245: Organotransition metal chemistryo o
Page 246 and 247: 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 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 298 and 299: Five electron ligandsFerrocene unde
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
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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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