2 Homometallic Alkoxides

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arium oxo-alkoxides, hexanuclear 398 barium tert-butoxide 398 barium titanium oxo-alkoxides, structures of 398 barium titanium oxo-isopropoxide 398 barium triphenylcarbinolate 240 barium triphenylsiloxide ligand 239 barium tris-tert-butylsiloxide 240 barium-titanium-ethoxide systems 205 benzene 22, 31, 35, 93, 120 benzoylacetone 119, 120, 121, 210 benzyltungsten isopropoxide diketonate 291 beryllium 186, 207 beryllium di-n-propoxide 59 beryllium di-tert-butoxide 59, 80 beryllium dimethylberyllium 49 NMR spectra of alkylberyllium tert-butoxides 81 beryllium see also alkaline earth metals; barium; calcium; magnesium; strontium beryllium alkoxides 32, 41, 46, 59, 80, 132 beryllium aryloxides 516 beryllium dialkoxides 60, 234 beryllium hydride 59 beryllium methoxide 29 beryllium triethylcarbinol 234 bi-octahedral units 231 confacial 293, 294, 298, 336, 337 edge-sharing 202, 294, 356 bimetallic alkoxides, homoleptic 185 bimetallic alkoxometallates 192 bipyramidal configuration 297 bismuth 186, 446 bismuth alkoxides 28, 40, 250, 251 bismuth aryloxides 636, 650, 651–652 bismuth lead strontium calcium copper oxide 674 bismuth strontium calcium copper oxides 674 bismuth trialkoxides 73 boron 124, 125, 126, 186 boron alkoxides 3, 31, 32, 35, 38, 55, 69, 70, 145 boron chlorides 20 boron N,N-diethylaminooxide derivatives 126 boron isopropoxide 74 boron trichloride 38, 39 boron triphenoxide, vapour pressures of 70 boron tris(tetrahydrofurfuroxide) 70 bromine, titanium tetra-n-butoxide 130 butterfly configuration 288, 289, 299 tert-butyl hydroperoxide 676, 677, 679 n-butyl lithium 675 tert-butyl peroxo titanatrane 677 2,4,6-di-tert-butylphenoxide 479 Index 689 2,6-di-tert-butylphenoxide 480, 481, 560, 561, 614, 631 butyraldehyde 143, 144 C cadmium 331, 338 cadmium alkoxides 80, 331–333, 332, 364, 365–366 cadmium aryloxides 631, 634 cadmium ethoxide 29 caesium see also alkali metals; lithium; potassium; rubidium; sodium caesium aryloxides 515 caesium methoxide 234 caesium phenoxide 509 caesium tert-butoxide derivatives 58 caesium trifluoromethoxides 58 calcium 15 see also alkaline earth metals; barium; beryllium; magnesium; strontium calcium alkoxides 41, 145, 238, 348–352 calcium aryloxides 517 calcium dialkoxides 60, 238 calcium oxo-ethoxide, hexanuclear 398 calixarenes 111, 445, 452–453 Cannizzaro reaction 141, 142 carbamates 134, 136 carbodiimides 134, 293 carbon dioxide 134, 483–484, 631 carbon monoxide 137, 477 insertion of 297, 482–483 reactions with homometallic alkoxides 150, 154 carbonylation 297, 482–484 carboxylic acids 106, 674 catalysts 4, 15, 671 Lewis acid 633 metal alkoxides as 675 metathesis 678 Ziegler-Natta type 675 catechols 445, 449 ceramic materials 31, 185, 674, 680 precursors for 671 synthesis of 3, 109 ceric ammonium nitrate 24 cerium 258–261, 274, 399 dipyridinium hexachloro derivatives of 23 organometallic compounds 140 tetraisopropoxoaluminates of 210 see also dysprosium; erbium; europium; gadolinium; holmium; lanthanide metals; lutetium; neodymium; praseodymium; samarium cerium alkoxides 32, 65, 66, 259 cerium isopropoxide 65, 404
690 Index cerium oxo-isopropoxide 388 cerium tert-alkoxides, heteroleptic 45 cerium tert-butoxide, synthesis of 26 cerium tetra-alkoxides 23, 65 cerium tetraisopropoxide 36 cerium tetrapentyloxide 65 Chemistry of Double <strong>Alkoxides</strong> of Various Elements 183 3-(5-chlorosalicylidene amino)propanolate 320 chlorotitanatrane, monomeric 271 chromium 75, 192, 280, 612 chromium alkoxides 26, 30, 40, 46, 68, 95, 280, 300–319, 362–363 chromium aryl tricarbonyl, photooxidation of 45 chromium aryloxides 584–586 chromium dichloride monomethoxide dimethanolate 94 chromium dichloride monomethoxide monomethanolate 94, 98 chromium dimethoxide 98 chromium ethoxide 18, 95 chromium group alkoxides, heterometallic 357–361 chromium methoxide 75, 95, 136 chromium oxo-alkoxides 419 chromium tetra-tert-butoxide 45, 68, 94, 97 chromium tetrakis-(2,2,4,4-tetramethyl-3pentanolate) 280 chromium tri-tert-butoxides 68 chromium trialkoxides 68 chromium trichloride 30 chromium triethoxide 98 chromium trimethoxide 45, 98 chromium-tert-butoxide, cyclopentadienyl 280 chromyl(VI) alkoxides 88 cobalt 75, 192, 361 cobalt alkoxides 18, 46, 68, 321, 322, 361, 362–363 cobalt aryloxides, simple 617 cobalt bromide methoxide 96, 100 cobalt chloride methoxide 96 cobalt dichloride 30 cobalt dimethoxide 95, 96, 98 cobalt iodide methoxide 96, 100 cobalt methoxide 75, 100, 135 cobaltodisiloxanes, trinuclear 335 copper 75, 186 copper(II) acetylacetonate-methoxide, dimeric 135 copper alkoxides 32, 183, 327, 329–330 alcohol-interchange reactions 110 heterometallic 361, 362–363 homoleptic 46, 329 synthesis of 18 copper(II) alkoxyalkoxides 113 copper aryloxides 484, 626, 627–629, 631 copper bromide methoxide 101 copper chloride alkoxides 101 copper diethoxide, magnetic moments of 100 copper dimethoxide 96, 98, 100, 101 copper fluoroalkoxides 27, 110 copper methoxide 18, 29, 75, 101, 110 copper oxo-alkoxides 432, 433–434, 435 copper(I) tert-butoxide 110, 135 copper zirconate derivatives 192 copper-4-methylphenoxide bond 484 crotonaldehyde 294 Curie-Weiss law 97, 98, 100, 101 cyclohexadiene 562, 563, 611, 612, 626 1,3-cyclohexadienone 447, 478 cyclohexane 38, 63, 85, 672 trans-1,2-cyclohexanediolate bridges 274 cyclohexanol 44, 672 cyclohexanone 147, 672 cyclohexene 672 cyclohexenylphosphines 611 cyclohexylphosphines 611 cyclometallation 480, 481, 482 1,3-cyclooctadiene 563 cyclopentanol 44 D d-block metal alkoxides 24, 32, 191 d-block metal aryloxides 457 d-block metals 26–28, 116 dialkyl selenite 36 dialkylamides 460, 538 dialkylamines 39, 461 2,6-dialkylphenols 518 2,6-dialkylphenoxide 562 2-(dialkylphosphino)phenoxides 447 diamagnetism 428, 472 diamines 127, 450, 451 1,3-diaminopropane 451 2,6-diarylphenols 574 2,6-diarylphenoxide 562 dibenzoyl methane 120, 121, 210 dichlorogallane 50 dichloromethane 20 2,6-di(chloromethyl)phenols 449 dichlorotetramethoxo tungsten(VI) complex 289 Diels-Alder reactions 502, 560, 562, 635, 680 diethyl selenite 36 N,N-diethylhydroxylamine 125, 126, 127 2,6-diformyl phenols 449
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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
Page 637 and 638: 637 Table 6.48 Aluminium aryloxides
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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: 688 Index alkoxometallate(IV) ligan
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 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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