2 Homometallic Alkoxides

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thallium compounds, reaction with lanthanide metals 454 thallium phenoxide 484 thallous ethoxide 17 thermodynamic data 55–73 thermolysis 671, 675 THF (tetrahydrofuran) 15, 48, 141, 253, 390, 454, 516 thiocarbonate 483 thiols, reactions of metal alkoxides with 130 2-thiophenoxides 449 thioranes, ring-opening polymerization 679 thiotungsten tetra-tert-butoxide compound 290 thorium 22, 186, 266–267, 537 monomeric tert-butoxide 266 thorium(IV), tetraisopropoxoaluminates of 210 thorium see also actinide metals; neptunium; plutonium; uranium thorium alkoxides 32, 55, 65, 82–84, 266, 267 tertiary 66 thorium aryloxides 533, 537 thorium isopropoxide 65, 187 thorium(IV) isopropoxide complex, tetrameric 26 thorium(IV) metal centres 481 thorium tetra-alkoxides 22, 23, 65 thorium tetrachloride 23 thorium tetrahalides 130 thorium trialkoxide monochlorides 23 tin 124, 125, 186, 274, 437 alkyltin alkoxides 74 alkyltin chlorides 28 alkyltin triisopropoxides 120 alkyltin tris-acetylacetonates 120 dibutyltin dimethoxide 73 tin alkoxides 32, 35, 55, 72, 106, 114, 115, 130, 145, 246, 248–249 heterometallic 365–366 homometallic 28 hydrolysis of 384 organometal 31, 32 tin aryloxides 473, 636, 649–650 tin(II) ˇ-diketonates 121 tin(IV) cadium oxo-neopentyloxide acetate molecule, heterometallic 437 tin(II) dimethoxide 121 tin(II) ethyleneglycollate 246 tin homoleptic tetrakis-beta-diketonates 119 tin hydrides 614 tin isopropoxide 72 tin oxo-alkoxides 384, 433–434 tin(IV) oxo-isobutoxide, trinuclear 437 tin(II) oxo-methoxide, hexanuclear 437 tin(IV) oxo-tert-butoxide acetate 437 Index 701 tin tert-amyloxide 72 tin tert-butoxide 72 tin tetra-alkoxides 28, 131 tin tetrachloride 28 tin tetraethoxide 28 tin tetraisopropoxide 36, 120, 247 tin tetraisopropoxide isopropanolate 35 tin trichloride monoethoxide, alcoholate of 28 Tischtchenko reactions 108, 142–145, 679 titana-norbornene compounds, intermediate 562 cis-anti-cis-titanacycle 563 titanacyclohept-3-ene 563 titanacyclopent-3-ene 563 titanacyclopentane 562, 563 titanacyclopropane 563 titanatrane, mononuclear isopropoxy 677 titancyclopentadiene 562 titanium 51, 106, 124, 125, 186, 219, 334, 353–356, 538, 673 infrared spectra 73 titanium di-methyl substrates 562 titanium bimetallic derivatives 200 binol-type ligands and 502 coordination number 119 dialkoxo-bis-acetylacetonates 272 hexafluoroacetylacetonate derivatives 120 monomeric tert-butoxides 70 N, N-diethylaminooxides 126 organometallic chemistry of 560 organotitanium alkoxides 273 titanium acetyl chloride 131 titanium alkoxides 32, 33, 55, 65, 84, 119, 120, 122, 128, 130, 132, 145, 268, 276–279, 385, 675, 676, 677, 679 alcoholysis reactions of 110 alkali 26 bis-cyclopentadienyl 274 heterometallic 358–360, 411 hydrolysis of 384 mononuclear 274 preparation of 37 tertiary 66 thermodynamic properties of 63, 63 titanium amyloxides, tertiary 56 titanium aryloxides 477, 538, 539–554, 563 titanium carbide 680 titanium complexes, chiral 680 titanium coordination, octahedral 409 titanium dialkoxide dicarboxylates 122 titanium dialkylamides 130 titanium dibromide, spectrum of 33 titanium dichloride 560 titanium dichloride dialkoxide alcoholates 271
702 Index titanium dichloride diethoxide 131 titanium diethoxide, bis-benzyl 273 titanium N,N-diethylaminooxide derivatives 126 titanium diisopropoxide dialkyltartrate complex 676 titanium dimethylamide 271 titanium ethoxide 62, 63, 84, 88, 105, 123, 391 titanium group alkoxides, heterometallic 353–357 titanium homoleptic tetrakis-beta-diketonates 119 titanium isopropoxide 62, 84, 123, 146, 213, 677, 680 titanium isopropylthiolate 271 titanium methoxide 57, 61 titanium monochloride tributoxide, trimeric 61 titanium monochloride triethoxide 131 titanium monoethoxide diethyltartrate diphenyl hydroxamate complex 676 titanium n-butoxide 84, 105 titanium n-propoxide 84 titanium neopentyloxide 201 titanium nitride 680 titanium oxo-alkoxides 384, 390, 393, 405 titanium oxo-ethoxide 405 titanium sub-group metal oxo-alkoxides 405–412 titanium tartrate catalysts, dinuclear 271 titanium tert-butoxide 33, 84 titanium tetra-acetate 123 titanium tetra-alkoxides 61, 62, 63, 105, 124, 133, 135, 268 hydrolysis of 384 preparation of 22 tetranuclear 233 titanium tetra-n-butoxide 61, 130 titanium tetra-tert-amyloxide 105 titanium tetra-tert-butoxide 87 titanium tetra-isopropoxide 105 titanium tetrachloride 50, 57, 133 titanium tetraethoxide 26, 33, 62, 131, 230, 384, 405 titanium tetrahalides 130 titanium tetraisobutoxide 84 titanium tetraisopropoxide 84, 384, 675–676, 677 titanium tetrakis(hexafluoroisopropoxide) 62 titanium tetrakis(triphenysiloxide) 112 titanium tetramethoxide 84 titanium tetravalent derivatives 60 titanium thiolates 130 titanium trialkanolaminates 677 titanium trialkylsiloxides, preparation of 37 titanium trichloride monoalkoxides 133 titanium trichloride monoethoxide 50 titanium trimethoxide 93 titanium trimethylsiloxide 112 titanium tris-glycolate 197, 273 titanium tritox methoxide, bis-methyl 273 titanium-niobium products 201 titanium-titanium, bond distance 538 titano-zeolite heterogeneous catalysts 677 titanosilsesquioxanes 273 toluene 31, 35, 151, 561 transesterification reactions 37, 38, 39, 203 trans-octahedral configuration, distorted 336 transition metal alkoxides 75, 109, 136, 140, 183, 677–680 transition metal antimony ethoxides 191 transition metal aryloxides 465, 482 transition metal complexes 212, 353, 673 transition metal oxo-alkoxide cluster molecules 396 transition metals 128, 208 transition metals see also cerium; lanthanide metals; dysprosium; erbium; europium; gadolinium; holmium; lutetium; neodymium; samarium trialkanolamines 116–117, 271, 677 trialkoxosilanes 74 trialkylaluminium 49 trialkylboron 49 trialkylsilanols 112 tributylgallium 46 tricalcium silicate 31 triethanolaminate, N-methyldiethanolaminate, gallium and 243 triethanolaminates 200 triethanolamine 205, 246, 390 triethoxysilicon monoacetate 121 4,4,4-trifluoro-1-phenyl-1,3-butanedionate (diket) 271 5,5,5-trifluoro-4-hydroxy-4-trifluoromethyl-2pentanone 261 trigonal bipyramidal (TBP) configurations 243, 268, 298, 299, 397, 411 trigonal pyramid configuration 404 trimetallic octanuclear complexes 338, 346 trimethylaluminium 464 trimethyltin cyclohexanone oximate 127 2,4,6-trinitrophenol (picric acid) 447, 455, 509 tris-cyclopentadienyl cerium tert-butoxide 259 tris(dialkylamide)monoalkyliminotantalum, alcoholysis of 39 tris(hydroxymethyl)ethane (THME) 272, 274 trisilanols, cubic 273 tris(organo)chromium complex 141
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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
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641 [Al(OAr) 2⊲i-Bu⊳] trigonal
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643 [Al(OAr)Cl(Me)⊲NH2But⊳] OC6
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645 Table 6.49 Gallium aryloxides B
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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 and 692: 692 Index gas-phase photoelectron s
Page 693 and 694: 694 Index lead tert-butoxide 386 Le
Page 695 and 696: 696 Index metal-hydrogen bonds clea
Page 697 and 698: 698 Index oxo-alkoxides 384, 385, 3
Page 699: 700 Index sodium hydroxide 142 sodi
Page 703: 704 Index X X-ray Absorption Near E
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2 Homometallic Alkoxides

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