2 Homometallic Alkoxides

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528 Table 6.19 (Continued) Bond length ( ˚A) Bond angle ( Ž ) Compound Aryloxide M–O M–O–Ar Ref. [CpSm(OAr)(fluorenone ketyl)(HMPA)] pseudo-tetrahedral Sm OC6H2But 2-2,6-Me-4 2.158 (6) 174 xlv [fSm⊲OAr⊳2⊲OEt2⊳g2⊲m-fluorenone pinacolate⊳] OC6H2But 2-2,6-Me-4 2.115 (3) 2.141 (5) 160 173 xliii, xlv [⊲ArO⊳⊲thf⊳3Sm⊲ -I⊳2Sm⊲OAr⊳⊲THF⊳3] 6-coord. Sm, OAr trans to -I OC6H2But 2-2,6-Me-4 2.300 (10) 179 xliv [⊲ArO⊳2⊲thf⊳Sm⊲ -Cl⊳2Sm⊲OAr⊳2⊲THF⊳] 5-coord. Sm, square pyramid with axial OAr OC6H2But 2-2,6-Me-4 2.135 (6) 2.110 (7) 165 167 xliv [Cp Ł Sm⊲OAr⊳⊲hmpa⊳2] psuedo-tetrahedral Sm OC6H2But 2-2,6-Me-4 2.345 (4) 164 xliv [Sm⊲OAr⊳2⊲I⊳⊲thf⊳2] tbp, axial THF OC6H2But 2-2,6-Me-4 2.153 (7) 164 xliv [Cp Ł Sm⊲ -OAr⊳2SmCp Ł ] 2-OC6H2But [Cp 3-2,4,6 2.425 (5), 2.512 (6) xlvi Ł 2Sm⊲OAr] possible agostic Sm–methyl interaction 2-OC6H2But 3-2,4,6 2.144 (5) 166 xlvi [( , 5-Cp Ł ⊳Sm⊲OAr⊳⊲ , 5-Cp Ł ⊳K⊲thf⊳2]1 infinite chain polymer 2-OC6H3But 2-2,6 2.29 (2) 175 xlvi [⊲ , 5-Cp Ł ⊳Sm⊲OAr⊳⊲ , 5-Cp Ł ⊳K⊲thf⊳2]1 possible agostic Sm–methyl interaction 2-OC6H2But 2-2,6-Me-4 2.330 (6) 127 xlvi [Eu⊲OAr⊳2⊲THF⊳3].THF tbp, axial THF OC6H2But 2-2,6-Me-4 2.321 (5) 2.337 (5) 174 175 xlvii [Eu⊲OAr⊳2⊲NCMe⊳4] distorted octahedron OC6H3But 2-2,6 2.313 (12) 2.35 (2) 174 175 xlviii [Eu⊲ 2-OAr⊳3Eu⊲OAr⊳].toluene Contains three 1-Ph–Eu and three 2 contacts -Ph–Eu OC6H3Ph2-2,6 2-OC6H3Ph2-2,6 2.361 (3) 2.493 (2), 2.463 (3) 2.517 (3), 2.426 (3) 2.428 (2), 2.438 (2) 155 xlix
529 [Eu⊲ 2-OAr⊳4⊲OAr⊳2⊲ 3-OH⊳2⊲NCMe⊳6] butterfly arrangement of Eu atoms OC6H3Pri 2-2,6 2-OC6H3Pri 2-2,6 [⊲DME⊳⊲ArO⊳Eu⊲ 2-OAr⊳3Eu⊲DME⊳2] [Eu⊲OAr⊳2⊲OH2⊳6]⊲OAr⊳.6H2O OC6H3Me2-2,6 2-OC6H3Me2-2,6 OC6H2⊲NO2⊳3-2,4,6 2.284 (6)–2.299 (6) 2.403 (6)–2.543 (6) 2.350 (5) 2.447 (5)–2.597 (5) 2.327 (7) 2.372 (7) 167 151 151 xlviii l xv [⊲L⊳3Eu⊲ 2-OAr⊳3Eu⊲L⊳2⊲OAr⊳] L D N -methylimidazole; face-shared bi-octahedron [⊲L⊳2⊲ArO⊳Eu⊲ 2-OAr⊳2⊲ 2-L⊳Eu⊲L⊳2⊲OAr⊳] L D NCMe; face-shared bi-octahedron f[Eu⊲ 3- OC6H3Me2-2,6 2-OC6H3Me2-2,6 OC6H3Me2-2,6 2-OC6H3Me2-2,6 2.365 (3) 2.479 (3)–2.632 (3) 2.288 (3) 2.479 (3)–2.632 (3) 158 178 li li 2-OCH2CH2OMe⊳⊲ 2- OCH2CH2OMe⊳⊲OAr⊳][H]g4 tetrahedral Eu OC6H3Me2-2,6 OC6H3Pri 2-2,6 derivative isostructural but poorly refined 2.420 (8) 154 lii [Gd⊲OAr⊳3⊲THF⊳2] tbp, axial THF OC6H3Pri 2-2,6 2.138 (9) 2.156 (11) 153 173 xxii 2.096 (9) 176 [Gd(OAr) 2⊲OH2⊳6]⊲OAr⊳.6H2O three forms OC6H2⊲NO2⊳3-2,4,6 2.309 (7) Form I 151 liii 2.363 (7) Form II 150 2.32 (1) 148 2.38 (1) Form III 148 2.34 (2) 148 2.38 (2) 147 xlviZ. Hou, Y. Zhang, T. Yoshimura, and Y. Wakatsuki, Organometallics, 16, 2963 (1997). xlviiJ. R. van den Hende, P.B. Hitchcock, S.A. Holmes, M.F. Lappert, WingPor Leung, T.C.W. Mak, and S. Prashar, J. Chem. Soc., Dalton Trans., 1427 (1995). xlviiiW.J. Evans, M.A. Greci, and J.W. Ziller, J. Chem. Soc., Dalton Trans., 3035 (1997). xlixG.B. Deacon, C.M. Forsyth, P.C. Junk, B.S. Skelton, and A.H. White, Chem. Eur. J., 5, 1452 (1999). lW.J. Evans, W.G. McClelland, M.A. Greci, and J.W. Ziller, Eur. J. Solid State Inorg. Chem., 33, 145 (1996). liW.J. Evans, M.A. Greci, and J.W. Ziller, J. Chem. Soc., Chem. Commun., 2367 (1998). liiW.J. Evans, M.A. Greci, and J.W. Ziller, Inorg. Chem., 37, 5221 (1998). liiiJ.M. Harrowfield, L. Weimin, B.W. Skelton, and A.H. White, Aust. J. Chem., 47, 349 (1994). (continued overleaf )
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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
Page 477 and 478: Metal Aryloxides 477 as expected ar
Page 479 and 480: Metal Aryloxides 479 whereas R D Me
Page 481 and 482: where OAr = O But But H3C H3C O Ta
Page 483 and 484: PPh 2 Ph P Pt OAr PPh2 where OAr =
Page 485 and 486: 6 SURVEY OF METAL ARYLOXIDES 6.1 Sp
Page 487 and 488: 487 Na2[V(O) 2(OAr) 2]2.4H2O.DMF 6-
Page 489 and 490: 489 [Tc(O)(OAr)(di-OAr)] 8-quin 2.0
Page 491 and 492: 491 [Ni3⊲OAr⊳6][ClO4].EtOH 8-qu
Page 493 and 494: 493 [Pt(OAr⊳2](tcnq) sq. planar P
Page 495 and 496: 495 [Al(OAr) 3].MeOH 8-quin 1.850 (
Page 497 and 498: 497 [Sb(OAr) 2⊲S2COEt⊳] pentago
Page 499 and 500: 499 [Tc(O)(OAr)(N-salicylideneDD-gl
Page 501 and 502: Metal Aryloxides 501 A contribution
Page 503 and 504: 503 Table 6.8 Metal bi-phenolates B
Page 505 and 506: 505 Table 6.9 Metal binaphtholates
Page 507 and 508: 507 [TiCl2(di-OAr)]2 two tetrahedra
Page 509 and 510: Metal Aryloxides 509 co-workers hav
Page 511 and 512: 511 [Li⊲ 2-OAr⊳]3 planar Li3O3
Page 513 and 514: 513 Table 6.11 Sodium aryloxides Bo
Page 515 and 516: Table 6.12 Potassium aryloxides Met
Page 517 and 518: Table 6.15 Magnesium aryloxides Met
Page 519 and 520: 519 Table 6.18 Barium aryloxides Bo
Page 521 and 522: 521 Table 6.19 Group 3 metal and la
Page 523 and 524: 523 [Me4N]La2Na2⊲ 4-OAr⊳⊲ 3-O
Page 525 and 526: 525 [Nd⊲OC6H3Ph- 6-C6H5⊳⊲OC6H
Page 527: 527 [⊲THF⊳Li⊲ 2-OAr⊳2Sm⊲C
Page 531 and 532: 531 [Yb(OAr) 3⊲THF⊳2].THF squar
Page 533 and 534: Metal Aryloxides 533 carbon atoms a
Page 535 and 536: 535 [Cp Ł Th(OAr)⊲CH2SiMe3⊳2]
Page 537 and 538: Metal Aryloxides 537 amido compound
Page 539 and 540: 539 Table 6.21 Titanium aryloxides
Page 541 and 542: 541 [Ti2⊲ 2-OAr⊳2(OAr) 2Cl4]2 e
Page 543 and 544: 543 [Ti(OAr) 2⊲NMe2⊳2] tetrahed
Page 545 and 546: 545 [Ti(OAr) 3Bu t ] tetrahedral Ti
Page 547 and 548: 547 [⊲ArO⊳2Ti⊲ 2-ButNDCC4Et4C
Page 549 and 550: 549 [Cp⊲C5H3Me-Pri-1,2)Ti(OAr)Cl]
Page 551 and 552: 551 [CpTi(OAr) 2⊲HPPh⊳] OC6H3Pr
Page 553 and 554: 553 [Ti⊲di-OAr⊳Cl2].THF 6-coord
Page 555 and 556: 555 Table 6.22 Zirconium aryloxides
Page 557 and 558: 557 [Zr(Ind-OAr) 2] 1-indenylphenox
Page 559 and 560: 559 [Cp2Zr(OAr)] 18-electron Zr, tw
Page 561 and 562: Metal Aryloxides 561 The thermal st
Page 563 and 564: Metal Aryloxides 563 can only arise
Page 565 and 566: 565 1.839 (2) 138 1.854 (2) 140 [(t
Page 567 and 568: 567 [V(OAr) 3-N-Li(THF) 3] tetrahed
Page 569 and 570: 569 [V(O)(di-OAr)] 6-coord. V, both
Page 571 and 572: 571 cis,mer-[Nb(OAr) 2Cl3(THF)] dis
Page 573 and 574: 573 [Nb⊲OC6H3Ph- 4-C6H7⊳⊲OAr
Page 575 and 576: 575 Table 6.26 Tantalum aryloxides
Page 577 and 578: 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
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Metal Aryloxides 649 Table 6.53 Tin
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651 Table 6.56 Bismuth aryloxides B
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REFERENCES Metal Aryloxides 653 1.
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Metal Aryloxides 655 56. Y. Nakayam
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Metal Aryloxides 657 123. T.W. Coff
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Metal Aryloxides 659 202. A. Bell,
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Metal Aryloxides 661 268. K. Ishiha
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Metal Aryloxides 663 341. B.S. Kali
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Metal Aryloxides 665 405. P.N. Rile
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Metal Aryloxides 667 483. Y. Hayash
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Metal Aryloxides 669 561. A.P. Shre
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688 Index alkoxometallate(IV) ligan
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690 Index cerium oxo-isopropoxide 3
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692 Index gas-phase photoelectron s
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694 Index lead tert-butoxide 386 Le
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696 Index metal-hydrogen bonds clea
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698 Index oxo-alkoxides 384, 385, 3
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700 Index sodium hydroxide 142 sodi
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702 Index titanium dichloride dieth
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704 Index X X-ray Absorption Near E
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2 Homometallic Alkoxides

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