2 Homometallic Alkoxides

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[W2⊲ -OMe⊳2⊲OMe⊳6⊲NPh⊳2] 6 1.89-1.92 (3) av. 1.91 2.05, 2.16 (2) 131–151 (t) av. 139 121, 128 (b) [W2⊲ -OEt⊳2⊲OEt⊳4Cl2⊲NPh⊳2] 6 1.835–1.865 (9) 2.003, 2.213 (8) 129.7, 139.0 (t) 118.6, 126.8 (b) 318 [W2⊲ -OMe⊳2⊲OMe⊳4⊲NC6H4Me⊳2] 6 1.886–1.922 (6) 2.072, 2.181 (6) 126.8–138.0 (t) 139 av. 1.902 av. 131.6 120.1, 125.1 (b) [W2⊲ -OPr i ⊳2⊲OPr i ⊳4⊲NC6H4Me⊳2] 6 1.905–1.927 (4) 2.029, 2.243 (3) 137.4, 138.3 (t) 319 av. 1.915 130.0, 132.1 (b) ⊲NBun 4⊳C [W2⊲ -OMe⊳⊲ -Cl⊳2Cl4⊲NPh⊳2] [W2⊲ -OPr 6 – 2.002, 2.024 (5) 134.3, 135.2 319 i ⊳2⊲OPr i ⊳6⊲NPh⊳2] 6 1.877, 1.932 (4) av. 1.908 2.039, 2.227 (4) 127.2–169.2 (t) av. 141.1 121.1, 124.1 (b) 279 [W2⊲ -OCMe2CMe2O⊳⊲O2C2Me4⊳4⊲NHPh⊳2] 6 1.85–2.00 (2) (c) av. 1.93 1.80 (2) (b) – 118–148 320 [W2⊲ -NHMeC2H4NHMe⊳⊲OEt⊳6] 511.88–1.97 (2) av. 1.92 – – 324 [W2⊲ -OCH2But⊳2⊲ -NC4Me4N⊳⊲OCH2But⊳4⊲py⊳] 6 1.870–1.967 (8) 2.037–2.226 (8) 127.2–132.6 (t) 325 av. 1.926 av. 2.119 av. 129.8 124.9–135.6 (b) av. 130.6 [W2⊲ -OPr i ⊳2⊲ -NMeC2H2CMeN⊳⊲OPr i ⊳5] 6 1.875–1.962 (7) 2.055–2.131 (7) 127.2–142.0 (t) 325 av. 1.915 av. 2.086 av. 133.3 128.6–146.4 (b) av. 138.8 [W2⊲ -OBu t ⊳⊲ -NCPhCHCH⊳⊲OBu t ⊳5] 5 1.878–1.913 (4) 2.058–2.107 (4) 133.3–151.0 (t) 325 av. 1.892 av. 144.9 137.6, 138.3 (b) 311 277 (continued overleaf )
312 Table 4.11 (Continued) M–O Bond lengths ( ˚A) Metal Bond angles ( Ž ) Compound coordination Terminal Bridging � MOC Reference [W2⊲ -OPr i ⊳2⊲ -NCPhCHCH2⊳⊲OPr i ⊳5] 6 1.851–1.953 (5) av. 1.908 2.025–2.184 (5) av. 2.096 133.3–141.2 (t) av. 135.9 133.0–145.9 (b) av. 138.6 [W2f -NNC⊲C6H4Me⊳2g2⊲OBu t ⊳6] 5 1.858–1.944 (9) – 138.9–146.0 305 av. 1.892 av. 143.6 [W2f -NPhCO⊲OBu t ⊳g2⊲OBu t ⊳4] 511.895, 1.942 (5) – 127.1, 154.3 243 [W2⊲ -OCNPh⊳⊲OBu t ⊳6] 511.851–1.932 (9) – 124.0–155.6 326 av. 1.887 av. 143.8 [W2f -PhCO⊲OBu t ⊳g⊲OBu t ⊳5⊲PMe⊳3] 511.85–2.07 (3) av. 1.967 – – 326 [W2f -N⊲C6H4Me⊳CN⊲C6H4Me⊳g⊲OBu t ⊳6] 511.848–1.950 (10) – 127.0–155.0 327 av. 1.903 av. 143.5 [W2f -N⊲C6H11-c⊳CN⊲C6H11-c⊳g⊲OBu t ⊳6] 511.860–1.959 (6) – 129.0–154.4 328 av. 1.905 av. 144.9 [W2⊲ -NPriCNPr i ⊳⊲OBu t ⊳6] 511.839–1.946 (13) – 129.0–155.0 328 av. 1.897 av. 144.5 [W2⊲ -O2COBu t ⊳2⊲OBu t ⊳4] 511.885–1.926 (14) – 125–159 329 av. 1.903 av. 140 [W2⊲ -O2CBu t ⊳2⊲OBu t ⊳4] 511.883–1.909 (12) (ButO) – 124.5, 150.3 ⊲Bu av. 1.890 2.091–2.177 (12) (carboxylate) av. 2.134 tO⊳ 330 117.1, 119.7 (carboxylate) [W2⊲ -O2CBu t ⊳2⊲OBu t ⊳2⊲NPri 2⊳2] 511.78, 1.92 (3) ⊲ButO⊳ 2.007–2.264 (26) (carboxylate) av. 2.148 – 160, 163 ⊲ButO⊳ 330 325
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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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Page 261 and 262: 260 Alkoxo and Aryloxo Derivatives
Page 265 and 266: 264 Table 4.7 Alkoxides of lanthani
Page 271 and 272: 270 Table 4.8 (Continued) M-O Bond
Page 277 and 278: 276 Table 4.9 Alkoxides of titanium
Page 279 and 280: 278 Table 4.9 (Continued) Bond leng
Page 301 and 302: 300 Table 4.11 Alkoxides of chromiu
Page 303 and 304: 302 Table 4.11 (Continued) Metal M-
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Page 317 and 318: 316 Table 4.11 (Continued) Metal M-
Page 323 and 324: 322 Table 4.12 Alkoxides of mangane
Page 333 and 334: 332 Table 4.16 Alkoxides of zinc, c
Page 341 and 342: 340 Table 4.17 (Continued) Coordina
Page 349 and 350: 348 Table 4.18 Bimetallic alkoxides
Page 355 and 356: 354 Table 4.19 Heterometallic alkox
Page 359 and 360: 358 Table 4.20 Heterometallic alkox
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362 Table 4.21 Heterometallic alkox
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366 Table 4.22 (Continued) Coordina
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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
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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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