2 Homometallic Alkoxides

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[W2⊲ -CSiMe3⊳⊲ -CHCHCSiMe3⊳⊲OPri⊳4] 411.851–1.894 (8) – 140.8–169.4 340 av. 1.873 av. 152.9 [W2⊲ -CSiMe3⊳⊲ -CCSiMe3⊳⊲OPri⊳4⊲NC6H3Me2⊳] 4 and 511.851–1.921 (5) av. 1.897 – – 341 [W2⊲ -OPr i ⊳2⊲OPri⊳2⊲CH2Ph⊳2⊲C2Me2⊳2] 51av. 1.85 (1) av. 2.15 – 342 [W2⊲ -C4Me4⊳⊲ -CH2Ph⊳⊲OPri⊳4] 41av. 1.89 (2) – – 342 [W2⊲ -OBu t ⊳⊲ -C2Me2⊳⊲OBut⊳5⊲CO⊳] 51av. 1.90(2) av. 2.065 (10) – 343 [W2⊲ -C3H4⊳⊲OBut⊳6] 411.866–1.933 (5) – 140.0–150.8 344 av. 1.893 av. 144.7 [W2⊲ -OBu t ⊳2⊲ -C3H4⊳⊲OBut⊳4⊲ 2-C3H4⊳] 611.849–1.961 (7) 1.985–2.306 (7) 144.5–158.4 (t) 344 av. 1.898 av. 2.119 av. 151.9 132.8–141.1 (b) av. 136.9 [W2⊲ -OBu t ⊳2⊲ -C3H4⊳⊲OBut⊳4⊲CO⊳2] 611.857–1.96 (3) 1.967–2.315 (26) 140.0–168.2 (t) 344 av. 1.889 av. 2.143 av. 155.3 127.9–141.5 (b) av. 134.6 [W2⊲ -OCH2But⊳⊲ -C2H2⊳⊲OCH2But⊳5⊲py⊳2] 611.911–1.979 (17) 2.012, 2.070 (12) 129.8–139.6 (t) 345 av. 1.947 av. 134.7 132.7, 133.9 (b) [W2⊲OCH2But⊳⊲ -C2Et2⊳⊲OCH2But⊳5⊲py⊳] 611.848–1.989 (12) 2.055, 2.120 (6) 115.7–144.8 (t) 345 av. 1.930 av. 133.9 125.6, 128.4 (b) [W2⊲ -OCH2But⊳4⊲OCH2But⊳2⊲ 2-C2H4⊳2] 611.88, 1.89 (1) 2.31 (1) (long, av.) 2.00 (1) (short, av.) – 346 [W2⊲ -OPr i ⊳3⊲OPri⊳3f 2-⊲CH2⊳4g⊲ 2-C2H4⊳] 611.806–1.938 (8) 2.146 (8) (long, av.) 132.4–164.7 (t) 347 av. 1.889 2.056 (8) (short, av.) 136.1–145.4 (b) 315 (continued overleaf )
316 Table 4.11 (Continued) Metal M–O Bond lengths ( ˚A) Bond angles ( Ž ) Compound coordination Terminal Bridging MOC � Reference [W2⊲ -OPr i ⊳⊲OPri⊳5f , 2-C⊲CH2⊳3g⊲py⊳] 5 and 6 1.887–1.929 (5) 2.028, 2.156 (5) 133.7–144.7 (t) 347 av. 1.901 131.3, 144.1 (b) [W2⊲ -OPr i ⊳2⊲OPri⊳2⊲C3H7⊳2⊲ 2-C2Me2⊳2] 511.88 (1) 2.05, 2.15 (1) 138.9 (b) 348 [W2⊲ -OPr i ⊳2⊲OPri⊳2⊲CH2Ph⊳2⊲ 2-C2Me2⊳2] 511.856, 1.857 (4) 2.153 (4) (long, av.) 2.072 (4) (short, av.) 137.8, 145.3 (t) 349 [W2⊲ -OPr i ⊳2⊲OPri⊳2⊲Ph⊳2⊲ 2-C2Me2⊳2] 511.850, 1.866 (6) 2.170 (5) (long, av.) 2.088 (5) (short, av.) 139.2, 151.0 (t) 349 [W2⊲ -OPr i ⊳2⊲OPri⊳2⊲CEt⊳2⊲CH2But⊳2] 5 1.882 (5) 2.365 (5) (long) 1.961 (5) (short) 134.6 (t) 349 [Me2⊲ButO⊳W⊲ -OBu t ⊳⊲ -C2Me2⊳W⊲OBut⊳2⊲py⊳] 611.873–1.917 (9) 2.046, 2.064 (9) 146.4–158.7 (t) 349 av. 1.897 138.1, 142.7 (b) [W2⊲ -CPh⊳⊲ , 2-C4Me4⊳H⊲OPri⊳4] 611.870–1.925 (18) av. 1.896 – 130.6–155.0 350 [W2⊲ -CSiMe3⊳⊲ , 2-C4Me4⊳⊲OPri⊳4⊲CH2SiMe3⊳] 5 and 6 1.883–1.934 (5) av. 1.904 – 140.7–150.0 350 [W2⊲ -C2Me2⊳2⊲OPri⊳4] 611.871, 1.920 (14) – 142.4, 144.9 351 [W2⊲ -OCH2But⊳2⊲ , 2-C4H6⊳⊲OCH2But⊳4⊲py⊳] 611.909–2.049 (7) 2.078–2.146 (7) – 352 av. 1.966 av. 2.100 [W2⊲ -OCH2But⊳4⊲OCH2But⊳2⊲ 2-C2H4⊳2] 611.885, 1.892 (7) 1.993 (7) (short, av.) 130.5, 181.7 (t) 353 2.308 (7) (long, av.) 127.7–136.5 (b) [⊲ButO⊳3W⊲ -C2⊳W⊲OBut⊳3] 411.859–1.887 (10) av. 1.875 – 137.4–146.4 354 [W2f -CCCNH⊲C6H3Me2⊳g⊲OSiMe2But⊳5fCN⊲C6H3Me2⊳g4] 5, 6 1.93–2.07 (2) av. 1.98 – 129.1–157.5 335 [W2⊲ -CCHCHMe⊳⊲ -OSiMe2But⊳⊲OSiMe2But⊳5H] 5 1.87–1.94 (1) 2.05, 2.10 (1) 153.7–162.9 (t) 356 av. 1.91 137.0, 143.3 (b) [W2f -CC⊲CH2⊳⊲CHCH2⊳g⊲ -OSiMe2But⊳⊲OSiMe2But⊳5H] 5 1.84–1.94 (1) 2.01, 2.11 (1) 155.5–164.9 (t) 356 av. 1.89 139.8 (b)
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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 265 and 266: 264 Table 4.7 Alkoxides of lanthani
Page 267 and 268: 266 Alkoxo and Aryloxo Derivatives
Page 271 and 272: 270 Table 4.8 (Continued) M-O Bond
Page 277 and 278: 276 Table 4.9 Alkoxides of titanium
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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 349 and 350: 348 Table 4.18 Bimetallic alkoxides
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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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