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

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Organometallic compounds of the transition elementsC?6Cr~i1 BVUJ18 1614 12 10 8 6 (eV)Fig. 6.11 He(I) UV-photoelectron spectrum of bis(benzene)chromium.An ionization from a non-bonding m.o. gives rise to a sharp line, because thedimensions ofthe neutra! molecule and the resulting ion are essentially the same.This means that a vertical transition from the zero vibrationallevel of the neutra!molecule on ionization leads to the ion in its zeroth vibrationallevel also (FranckCondon principle). lonization from a bonding m.o. leads to an ion of increaseddimensions, the potential energy surface of which does not lie vertically abovethat of the neutra! molecule. Vibrational fine structure, which for a largemolecule is not resolved, therefore accompanies the ionization peak. This effect isseen in the spectrum under discussion.6.2.3 Fragment analysisMolecules which contain two or more different types of ligand may be of lowoverall symmetry. While it is of course possible to perform molecular orbita!calculations on such structures, the results may not give a very clear picture ofthe bonding, especially to the non-theoretician. A useful approach, largelydeveloped by Hoffmann, is called 'fragment analysis'. This involves breaking themolecule down into fragments and calculating the shapes and energies of theorbitals associated with these fragments. Those orbitals which are not involved inholding together the atoms of the fragment, that is, the orbitals which areavailable for bonding to other ligands to forma real molecule, are called 'frontierorbitals'.This approach is first illustrated with reference to the common groupingM(C0) 3 • A metal hexacarbonyl such as Cr(C0) 6 possesses an octahedralstructure. The a-bonding skeleton can be considered as being derived from sixequivalent d 2 sp 3 hybrid metal orbitals and the u-ligand orbitals. A pyramidal ( C 3 v)M(C0) 3 fragment can be derived from an octahedron by removal ofthree facialligands, leaving three low lying acceptor orbitals directed towards the vacatedligand sites. These may be resolved (Fig. 6.12) into a hybrid orbita! along the z-206
yy.,(e)hy (o 1 )s, Pz> dzZdxz + Px( xz))~dyz + Py( yz)~-~-ohd2 sp3 hybridsFig. 6.12 Frontier orbitals of an M(CO), fragment.
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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
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
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
Page 258 and 259: Organotransition metal chemistry)--
Page 260 and 261: Organotransition metal chemistryR R
Page 262 and 263: Organotransition metal chemistry-co
Page 264 and 265: Organotransition metal chemistry4.
Page 266 and 267: Organotransition metal chemistry(b)
Page 268 and 269: 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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