2 Homometallic Alkoxides

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lanthanide metals; lutetium; neodymium; praseodymium; samarium holmium isopropoxides 60 hydrogen bromide 130 hydrogen chloride 16, 28, 36, 130, 131 hydrogen peroxide 674 hydroquinone (1,4-dihydroxybenzene) 449, 538 8-hydroxyquinoline (oxine) 118, 445, 447, 455, 485 I indium 17, 243, 393, 403 indium alkoxides 28, 32, 244–245, 364, 365–366 indium amides 41 indium aryloxides 645–646 infrared spectra 73–77, 391 iodine 15 iridium alkoxides 322, 324 iridium aryloxides 484, 619 iron 75, 124, 445 iron alkoxides 32, 37, 99, 132, 145, 192, 321, 322 iron aryloxides 605–607, 616 iron bromide alkoxides 99 iron butoxide 69 iron dimethoxide 95, 98 iron ethoxide 69 iron group alkoxides 321 iron(III) halide alkoxides 99 iron isopropoxide 69 iron methoxide 29, 75 iron monochloride dimethoxide 99 iron oxo-alkoxides 430–432 iron propoxide 69 iron tert-butoxide 69 iron trialkoxides 69, 99 iron-sulfur cluster chemistry 616 isocyanates 106, 134, 136 isocyanides 154, 561 isopropanol 275, 389, 390, 672 isopropoxide-beta-diketonates 119 isopropoxide-tert-butoxide, dimeric mixed 103 isopropoxides 25, 34, 118, 119, 133, 146, 150, 190, 204, 217, 428, 462 isopropanolate 36 isopropoxometallates, homoleptic heterometallic 193 isopropyl alcohols 16, 35, 36, 86, 122, 130 isothiocyanates 106, 134, 136 J Jahn-Teller effect 94 K Keggin unit 409, 410 beta-ketoamines 127, 129 beta-ketoester, bidentate 210 beta-ketoesters 106, 119, 120 ketones 50, 137, 147, 153, 679, 680 Index 693 L lanthanide alkoxides 1, 16, 41, 60, 82–84, 109, 132, 258–266, 679 preparation of 37 unfluorinated 22 lanthanide aryloxides 457, 518–533 lanthanide chloride 24 lanthanide fluoroalkoxides 22 lanthanide halides 19 lanthanide isopropoxides 60, 77, 102 lanthanide metal alkoxides, homoleptic 7–8 lanthanide metal oxo-alkoxides 400–402 lanthanide metal oxo-isopropoxides, tervalent 385 lanthanide metal tert-butoxides, infrared spectra 77 lanthanide metal tri-alkoxides 672 lanthanide metal trichlorides 25 lanthanide metal tris-acetylacetonates, preparation of 107 lanthanide metals 4, 40, 52, 119, 124, 148, 353, 435, 466, 472 anhydrous tris-beta-diketonates of 118 beta-ketoamine derivatives of 128 bimetallic isopropoxides of 187 synthesis of alkyl compounds of 533 lanthanide metals see also cerium; dysprosium; erbium; europium; gadolinium; holmium; lutetium; neodymium; samarium lanthanons 190, 203 lanthanum 230 lanthanum alkoxides 82, 258, 261, 354–355, 680 lanthanum isopropoxide 60 lanthanum methoxide 29 lanthanum niobium complex 353 lanthanum triethanolaminate 201 lanthanum tris-beta-diketonate 107 lanthanum tris-tert-alkoxides 82 lead(II) oxo-isopropoxide, hexanuclear 437 lead di-tert-butoxide 105 lead alkoxides 28, 31, 247, 248–249, 365–366 lead aryloxides 649–650 lead methoxide 18 lead oxo-alkoxides 393, 433–434 lead oxo-tert-butoxide, tetranuclear 396 lead reagents, arylation with 446
694 Index lead tert-butoxide 386 Lewis acids 39, 108, 184, 187, 560, 561, 633 Lewis bases 186, 267, 284, 364, 467, 509, 516, 533 ligand field theory 208 ligand-alkoxide compounds, mixed 101, 127 lithiatantasiloxane complex 334 lithium 218, 334–336, 404 see also alkali metals; caesium; potassium; rubidium; sodium lithium alkoxides 45, 46, 233–234, 675, 679 lithium aluminate 675 lithium aryloxides 509, 510–512, 516, 615 lithium chloride 29, 389 lithium dialkylamide 460 lithium ethoxide 389 lithium isopropoxide 389 lithium methoxide 29, 184, 233, 234, 389 lithium perfluoro tert-butoxides 57 lithium phenoxide 516 lithium phosphino-alkoxides 49 lithium reagents 574 lithium silicon vanadium oxide 675 lithium tert-butoxide 57, 79, 101 lithium titanium oxo-isopropoxide 397 lithium uranium methyl alkoxide 140 lithium-bridged spirocyclic magnesiasiloxane complex 334 lutetium 266 see also cerium; dysprosium; erbium; europium; gadolinium; holmium; lanthanide metals; neodymium; praseodymium; samarium lutetium alkoxides 140 lutetium isopropoxide 60 M magnesium 4, 15, 48, 189 organomagnesium compounds 81 magnesium see also alkaline earth metals; barium; beryllium; calcium; strontium magnesium and alkaline earth metal alkoxides 241 magnesium and alkaline earth metal oxo-alkoxides 398–399 magnesium and alkaline earth metals, reactions of 189–190 magnesium alkoxides 41, 46, 80, 81, 145, 338, 348–352 magnesium aluminium silicates 675 magnesium antimony(III) complex 338 magnesium aryloxides 517 magnesium dialkoxides 48, 60 magnesium dimethoxide 145 magnesium hydride 48 magnesium methoxide 237 magnesium molybdenum(V) oxo-methoxide 398 magnetic susceptibility measurements 96–101 main group metals beta-ketoamine derivatives 128 heterometallic alkoxides of subvalent 221 organometallic compounds 139–141 manganese 75, 361 manganese acetate 614 manganese alkoxides 68, 320, 322, 361 manganese aryloxides 600–601, 614 manganese dimethoxide 95, 98 manganese heterometallic oxo-ethoxide 430 manganese methoxide 75 manganese sub-group metal oxo-alkoxides 428–430 mass spectral studies 101–105, 393–396 Meerwein-Ponndorf-Verley reactions 108, 141, 145–147, 148 mercuric chloride 16 mercury aryl-mercury reagents 518 reaction with lanthanide metals 454 mercury alkoxides 18, 32, 80, 332 mercury aryloxides, simple 634 mercury(II) chloride 15 mercury dimethoxide 136, 137 mercury ethoxide 29 mesityl-copper 630 metal alkoxide-glycolates 123 metal alkoxides 1, 3, 36, 37, 40, 50, 51, 77, 93, 101, 105, 106, 130, 131, 134, 138, 139, 150, 187, 385, 393, 461–462, 466, 538, 672, 674, 675 acidic 143 biheterometallic 183 X-ray crystal structures of 229–382 addition reactions of 193 applications of 1, 670–680 biheterometallic glycolate 197 bimetallic 186, 195 binary 28, 48, 126 chemistry of 1, 3, 25, 54, 105–155, 445 commercial production of 18 difficult-to-synthesize 39 electrochemical synthesis 18 heteroleptic 4, 5, 14, 23, 37, 50, 77, 79, 222 heterometallic 385 homoleptic 4, 5, 18, 19, 31, 50, 52, 77, 79, 109, 110, 138, 229, 230, 297 homoleptic Groups 4,5,7,9–16 8-13 homometallic 1, 3–181, 201, 203, 356 hydrolysis of 1, 109, 383–385
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Alkoxo and Aryloxo Derivatives of M
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1 Introduction In 1978 the book ent
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1 INTRODUCTION 2 Homometallic Alkox
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Homometallic Alkoxides 5 to complet
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Table 2.1 (Continued) Homometallic
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Homometallic Alkoxides 15 reactivit
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Homometallic Alkoxides 17 By contra
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Homometallic Alkoxides 19 2.3 React
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Homometallic Alkoxides 21 has been
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Homometallic Alkoxides 23 obtain on
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y Evans and co-workers: 160,161 Hom
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Homometallic Alkoxides 27 The heter
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Homometallic Alkoxides 29 not conve
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Homometallic Alkoxides 31 In view o
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2.7.2 Steric Factors Homometallic A
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Homometallic Alkoxides 35 (b) When
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Homometallic Alkoxides 37 2.8 Trans
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Homometallic Alkoxides 39 with orga
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2.9.1.1 Alkoxides of Be, Mg, Ca, Sr
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MfN⊲SiMe3⊳2g2thfx C2HOR, Cpy !C
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Homometallic Alkoxides 45 2.10 Misc
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Zr⊲CH2Bu t ⊳4 C 4RfOH benzene !
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2.10.5 By Insertion of Oxygen into
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Homometallic Alkoxides 51 First hom
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O M R M OR M OR RO M (M = Tl; R = M
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Homometallic Alkoxides 55 3. Nuclea
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Homometallic Alkoxides 57 explain t
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Decomposition (%) 100 80 60 40 20 0
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Table 2.6 Volatilities of tetravale
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Homometallic Alkoxides 63 deduced t
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Table 2.10 Vapour pressure of Ti, Z
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Homometallic Alkoxides 67 Table 2.1
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3.2.10 Alkoxides of Later 3d Metals
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Homometallic Alkoxides 71 Table 2.1
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Homometallic Alkoxides 73 affected
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Homometallic Alkoxides 75 the range
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Homometallic Alkoxides 77 several c
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Homometallic Alkoxides 81 In toluen
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Bu t O Bu t O Bu t O Th O O Bu O t
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Homometallic Alkoxides 85 1H NMR st
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Homometallic Alkoxides 87 septet wa
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Homometallic Alkoxides 89 experimen
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Table 2.21 1 H NMR spectra of Al4(O
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Homometallic Alkoxides 93 3.5 Elect
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Homometallic Alkoxides 95 ligand fi
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Homometallic Alkoxides 97 susceptib
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10 −1 /xM 12 10 −200 −100 0 [
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Homometallic Alkoxides 101 alkoxide
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Homometallic Alkoxides 103 fragment
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Homometallic Alkoxides 105 The mass
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Homometallic Alkoxides 107 [Al⊲OP
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Homometallic Alkoxides 109 Under ca
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4.3.2 Phenol-Alcohol Exchange React
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4.4 Reactions with Alkanolamines Ho
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Homometallic Alkoxides 115 R D Pr i
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Homometallic Alkoxides 117 La(OPr i
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Homometallic Alkoxides 119 with the
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Homometallic Alkoxides 121 about 1.
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Homometallic Alkoxides 123 concentr
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Homometallic Alkoxides 125 and othe
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Homometallic Alkoxides 127 Interest
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OH Monofunctional bidentate HC N R
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Homometallic Alkoxides 131 metal al
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Homometallic Alkoxides 133 which yi
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shown in Eq. (2.286): O Mo2(OEt)6 H
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Homometallic Alkoxides 137 Phenyl i
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Homometallic Alkoxides 139 The 1990
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Eqs (2.312)-(2.315): where R D l-ad
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Homometallic Alkoxides 143 On the b
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Homometallic Alkoxides 145 The form
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Homometallic Alkoxides 147 On furth
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4.16 Interactions Between Two Diffe
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4Mo2(OPr i )6 + 18CO (excess) Homom
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isolobality of CR 0 and W⊲OR⊳3
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W2(OR)8 (R = CH2Bu t ) + CO + H2C C
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Homometallic Alkoxides 157 43. J.S.
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Homometallic Alkoxides 159 122. P.N
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Homometallic Alkoxides 161 201. A.
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Homometallic Alkoxides 163 281. R.C
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Homometallic Alkoxides 165 358. L.A
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Homometallic Alkoxides 167 430. M.R
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Homometallic Alkoxides 169 521. I.
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Homometallic Alkoxides 171 N.I. Koz
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Homometallic Alkoxides 177 876. J.
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Homometallic Alkoxides 179 966. H.
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Homometallic Alkoxides 181 1054. M.
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184 Alkoxo and Aryloxo Derivatives
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236 Table 4.1 (Continued) M-O Bond
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244 Table 4.3 Alkoxides of aluminiu
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248 Table 4.4 Alkoxides of germaniu
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256 Table 4.6 Alkoxides of scandium
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264 Table 4.7 Alkoxides of lanthani
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276 Table 4.9 Alkoxides of titanium
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278 Table 4.9 (Continued) Bond leng
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300 Table 4.11 Alkoxides of chromiu
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302 Table 4.11 (Continued) Metal M-
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316 Table 4.11 (Continued) Metal M-
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322 Table 4.12 Alkoxides of mangane
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332 Table 4.16 Alkoxides of zinc, c
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340 Table 4.17 (Continued) Coordina
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348 Table 4.18 Bimetallic alkoxides
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354 Table 4.19 Heterometallic alkox
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394 Table 5.2 Chemical shifts from
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400 Table 5.3 Scandium, yttrium, la
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402 Table 5.3 (continued) Metal Oxo
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406 Table 5.4 Titanium and zirconiu
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420 Table 5.6 Chromium sub-group me
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1 INTRODUCTION 6 Metal Aryloxides T
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Metal Aryloxides 447 or both of the
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R1 OH O R2 R3NH2 −H2O Scheme 6.3
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Cl S N N OH O Cl Me 3C NH HN OH HO
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N OH N OH Me 3C Me3C HO HO N N OH H
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Metal Aryloxides 455 2Ln C 3Hg⊲C6
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Metal Aryloxides 457 Mixed halo, ar
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product metal aryloxide 1e,1f (Eqs
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Metal Aryloxides 461 Eqs 6.39 and 6
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O Mg Mg OAr O Metal Aryloxides 463
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3.7 From Metal Hydrides Metal Arylo
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Metal Aryloxides 467 Two other impo
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Metal Aryloxides 469 Table 6.1 Meta
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Table 6.3 W-OAr distances for vario
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Metal Aryloxides 473 At first it is
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Zr−O distance (Å) V−O distance
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Metal Aryloxides 477 as expected ar
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Metal Aryloxides 479 whereas R D Me
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where OAr = O But But H3C H3C O Ta
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PPh 2 Ph P Pt OAr PPh2 where OAr =
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6 SURVEY OF METAL ARYLOXIDES 6.1 Sp
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487 Na2[V(O) 2(OAr) 2]2.4H2O.DMF 6-
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489 [Tc(O)(OAr)(di-OAr)] 8-quin 2.0
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491 [Ni3⊲OAr⊳6][ClO4].EtOH 8-qu
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493 [Pt(OAr⊳2](tcnq) sq. planar P
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495 [Al(OAr) 3].MeOH 8-quin 1.850 (
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497 [Sb(OAr) 2⊲S2COEt⊳] pentago
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499 [Tc(O)(OAr)(N-salicylideneDD-gl
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Metal Aryloxides 501 A contribution
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503 Table 6.8 Metal bi-phenolates B
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505 Table 6.9 Metal binaphtholates
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507 [TiCl2(di-OAr)]2 two tetrahedra
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Metal Aryloxides 509 co-workers hav
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511 [Li⊲ 2-OAr⊳]3 planar Li3O3
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513 Table 6.11 Sodium aryloxides Bo
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Table 6.12 Potassium aryloxides Met
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Table 6.15 Magnesium aryloxides Met
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519 Table 6.18 Barium aryloxides Bo
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521 Table 6.19 Group 3 metal and la
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523 [Me4N]La2Na2⊲ 4-OAr⊳⊲ 3-O
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525 [Nd⊲OC6H3Ph- 6-C6H5⊳⊲OC6H
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527 [⊲THF⊳Li⊲ 2-OAr⊳2Sm⊲C
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529 [Eu⊲ 2-OAr⊳4⊲OAr⊳2⊲ 3
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531 [Yb(OAr) 3⊲THF⊳2].THF squar
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Metal Aryloxides 533 carbon atoms a
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535 [Cp Ł Th(OAr)⊲CH2SiMe3⊳2]
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Metal Aryloxides 537 amido compound
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539 Table 6.21 Titanium aryloxides
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541 [Ti2⊲ 2-OAr⊳2(OAr) 2Cl4]2 e
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543 [Ti(OAr) 2⊲NMe2⊳2] tetrahed
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545 [Ti(OAr) 3Bu t ] tetrahedral Ti
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547 [⊲ArO⊳2Ti⊲ 2-ButNDCC4Et4C
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549 [Cp⊲C5H3Me-Pri-1,2)Ti(OAr)Cl]
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551 [CpTi(OAr) 2⊲HPPh⊳] OC6H3Pr
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553 [Ti⊲di-OAr⊳Cl2].THF 6-coord
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555 Table 6.22 Zirconium aryloxides
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557 [Zr(Ind-OAr) 2] 1-indenylphenox
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559 [Cp2Zr(OAr)] 18-electron Zr, tw
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Metal Aryloxides 561 The thermal st
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Metal Aryloxides 563 can only arise
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565 1.839 (2) 138 1.854 (2) 140 [(t
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567 [V(OAr) 3-N-Li(THF) 3] tetrahed
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569 [V(O)(di-OAr)] 6-coord. V, both
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571 cis,mer-[Nb(OAr) 2Cl3(THF)] dis
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573 [Nb⊲OC6H3Ph- 4-C6H7⊳⊲OAr
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575 Table 6.26 Tantalum aryloxides
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577 [(THF)(ArO) 3Ta⊲DNND⊳Ta(OAr
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579 [Ta(OAr) 2Cl2⊲CH2C6H5⊳] tbp
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581 [Ta(OAr) 2Cl⊲ 6-C6Me6⊳] OC6
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583 [Ta(OAr)⊲OC6H3Pri- 2-CMeDCH2
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585 [f(TMEDA)Na⊲ 2-OAr⊳2g2Cr] 4
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587 Table 6.28 Molybdenum aryloxide
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589 [Mo2⊲OAr⊳5⊲NMe2⊳⊲HNMe
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591 [Mo(Hdi-OAr) 2] 6-coord. Mo, on
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593 [W2⊲OAr⊳6⊲HNMe2⊳2] OC6F
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595 [W(OAr) 2⊲DNBu t ⊳2] OC6H3P
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597 [W(OC6H3Ph- 1-C6H4⊳2⊲PMePh2
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599 [W⊲OC6HPh3- 1-C6H4-c-C5H8C- O
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601 [⊲OC⊳3Mn⊲C4H4N⊳Mn⊲CO3
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603 Table 6.32 Simple aryloxides of
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607 [NEt4]3fFe6⊲ 4-S⊳4⊲OAr⊳
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609 [Ru(OAr) 2(CO)(py-CMeO-4)] cis-
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Table 6.35 Simple aryloxides of osm
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Metal Aryloxides 613 states, e.g. [
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Bu t O Bu t (6-I) Bu t Bu t O Metal
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6.2.10 Group 9 Metal Aryloxides Met
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Table 6.38 Simple aryloxides of iri
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Metal Aryloxides 621 Table 6.39 (Co
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623 [Pd(OAr)⊲C6H3fCH2NMe2g2-2,6)]
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Metal Aryloxides 625 Table 6.41 Sim
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629 [(RNC) 2Cu⊲ 2-OAr⊳2Cu(CNR)
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Metal Aryloxides 631 The two-coordi
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Table 6.45 (Continued) Metal Arylox
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Table 6.47 Simple aryloxides of mer
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637 Table 6.48 Aluminium aryloxides
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639 [⊲ArO⊳2Al⊲ -OAr⊳2Mg(THF
Page 641 and 642: 641 [Al(OAr) 2⊲i-Bu⊳] trigonal
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Page 645 and 646: 645 Table 6.49 Gallium aryloxides B
Page 647 and 648: 647 Table 6.50 Indium aryloxides Bo
Page 649 and 650: Metal Aryloxides 649 Table 6.53 Tin
Page 651 and 652: 651 Table 6.56 Bismuth aryloxides B
Page 653 and 654: REFERENCES Metal Aryloxides 653 1.
Page 655 and 656: Metal Aryloxides 655 56. Y. Nakayam
Page 657 and 658: Metal Aryloxides 657 123. T.W. Coff
Page 659 and 660: Metal Aryloxides 659 202. A. Bell,
Page 661 and 662: Metal Aryloxides 661 268. K. Ishiha
Page 663 and 664: Metal Aryloxides 663 341. B.S. Kali
Page 665 and 666: Metal Aryloxides 665 405. P.N. Rile
Page 667 and 668: Metal Aryloxides 667 483. Y. Hayash
Page 669 and 670: Metal Aryloxides 669 561. A.P. Shre
Page 671 and 672: 672 Alkoxo and Aryloxo Derivatives
Page 687 and 688: 688 Index alkoxometallate(IV) ligan
Page 689 and 690: 690 Index cerium oxo-isopropoxide 3
Page 691: 692 Index gas-phase photoelectron s
Page 695 and 696: 696 Index metal-hydrogen bonds clea
Page 697 and 698: 698 Index oxo-alkoxides 384, 385, 3
Page 699 and 700: 700 Index sodium hydroxide 142 sodi
Page 701 and 702: 702 Index titanium dichloride dieth
Page 703: 704 Index X X-ray Absorption Near E
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2 Homometallic Alkoxides

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