2 Homometallic Alkoxides

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423 ⊲NBu4⊳2[Mo5⊲O⊳4⊲ 5-O⊳⊲ -O⊳8⊲ - OMe⊳4⊲NO⊳⊲Na,dmf⊳] 5 (Na) 6 (Mo) t, 5, MoO(Na), 1.717–1.743 (8) av. 1.727, NaO(Mo), 2.39–2.60 (1), av. 2.50 MoO, 1.688–1.705 (7) (t), av. 1.700 Mo2O, 1.895–1.934 (6) ( ) av. 1.912 MoO, 2.131 (5) ( 5, ap) 2.312–2.398 (7) ( 5, bs) av. 2.341 MoO(Na), 1.697–1.723 (7), av. 1.710, NaO(Mo), 2.376–2.407 (9) av. 2.385 – 167b ⊲NEt4⊳[W⊲O⊳2⊲OCMe2CMe2O⊳⊲CH2But⊳] [W⊲O⊳⊲OBu 5 t 1.712, 1.720 (5) – 71 t ⊳4⊲thf⊳] [W⊲O⊳⊲OSiMe2Bu 6 t 1.77 (3) – 164 t⊳4⊲py⊳] [W⊲O⊳⊲OBu 6 t 1.68 (1) – 41 t ⊳2⊲OC10H5MeC10H5MeO⊳] [W2⊲O⊳2⊲ -O⊳2⊲OSiMe2Bu 5 t 1.662 (6) – 165 t⊳4⊲py⊳2] 6 t, WO, 1.72 (1) (t) W2O, 103.2 41 WO, 1.93, 1.95 (1) ( ) [W2⊲ -O⊳⊲ -OBu t ⊳⊲OSiMe2But⊳5⊲py⊳2] 5, 6 1.89, 1.96 (1) W2O, 80.7 41 [⊲PhN⊳⊲ButO⊳2W⊲ -O⊳⊲ -OBu t ⊳2W⊲NPh⊳⊲OBu t ⊳2] 6 1.937 (4) W2O, 104.3 40 [f⊲PhN⊳⊲HOC2Me4O⊳⊲OC2Me4O⊳Wg2⊲ -O⊳] 6 1.87, 1.92 (4) W2O, 157 166 [W2⊲O⊳2⊲ -OMe⊳2⊲OMe⊳6] 6 t 1.696, 1.702 (7) – 49 [W2⊲O⊳2⊲ -OC6H11-c⊳2⊲OC6H11-c⊳6 6 t 1.691 (4) – 49 [⊲CF3CO2⊳2⊲ButCH2O⊳2W⊲ -OCH2But⊳⊲ - 5, 6 t 1.694 (4) – 36 CMe2⊳W⊲O⊳⊲OCH2Bu t ⊳⊲py⊳] [⊲Bu t CH2O⊳3W⊲ -CH2Bu t ⊳2⊲ - CHC3H5-c⊳W⊲O⊳⊲OCH2Bu t ⊳⊲py⊳] 6 t 1.713 (5) – 37 (continued overleaf )
424 Table 5.6 (continued) Metal Oxo M–Oxo bond Mx–Oxo Compound coord. coord. lengths ( ˚A) bond angles ( Ž ) Reference [f⊲HOC2Me4O⊳⊲OC2Me4O⊳⊲O⊳Wg2⊲ -O⊳] 6 t, WO, 1.689 (7) (t) WO, 1.900 (2) ( ) [f⊲HOC7H12O⊳⊲c-C7H12O2⊳⊲O⊳Wg2⊲ -O⊳] 6 t, WO, 1.68, 1.71 (2) (t) WO, 1.89, 1.92 (2) ( ) [f⊲HOC8H14O⊳⊲c-C8H14O2⊳⊲O⊳Wg2⊲ -O⊳] 6 t, WO, 1.66, (2) (t) WO, 1.81, 2.00 (2) ( ) W2O, 161.4 73 W2O, 154.3 73 W2O, 154.6 73 [K2⊲18-crown-6⊳3][⊲Bu t O⊳3W⊲ -O⊳⊲ -H⊳W⊲OBu t ⊳3]2 5 WO, 1.916, 1.932 (12) ( ) – 26 [W3⊲ -O⊳2⊲OBu t ⊳8] 31 ,41 ,51 WO, 1.81–1.99 (2) ( ) av. 1.89 – 170 [W4⊲ -O⊳2⊲ -OPr i ⊳3⊲OPr i ⊳9] 31 ,41 ,61 WO, 1.845–2.008 (13) ( ) av. 1.913 W2O, 99.8, 101.9 35 [W4⊲ -O⊳⊲ -OPr i ⊳2⊲OPr i ⊳7Cl] 21 ,41 [W4⊲ 4-C⊳⊲ -O⊳⊲ -OCH2Bu WO, 1.921–1.924 (10) ( ) W2O, 95.6 72 t⊳4⊲OCH2But⊳8] 41 ,51 [W4⊲ 4-C⊳⊲ -O⊳⊲ -OPr WO, 1.926–1.933 (11) ( ) W2O, 89.0 38 i ⊳4⊲OPr i ⊳8] 41 ,51 [f⊲CO⊳⊲dmpe⊳2W.W⊲O⊳2g2⊲ -O⊳] 3 WO, 1.897, 1.956 (7) ( ) W2O, 89.4 38 1 ,51 t, WO, 1.73 (1) (t) WO, 1.88 (1) ( ) W2O, 180 171 [W6⊲ -O⊳4⊲ -CEt⊳2⊲OBu t ⊳10] 31 ,41 WO, 1.895, 1.896 (8) and 1.755, 2.119 (8) ( ) W2O, 99.6, 156.0 172 [W6⊲ -O⊳4⊲ -CPr n ⊳2⊲OBu t ⊳10] 31 ,41 WO, 1.878, 1.906 (9) and 1.774, 2.113 (9) ( ) W2O, 99.7, 159.6 164 [W8⊲ -O⊳4⊲ -OPr i ⊳4⊲OPr i ⊳12] 21 ,41 WO, 1.884–1.952 (10) ( ) av. 1.918 W2O, 97.8, 98.4 173 ap D apical, bs D basal, t D terminal. 1 Coordination number doubtful.
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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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Page 373 and 374: 372 Alkoxo and Aryloxo Derivatives
Page 395 and 396: 394 Table 5.2 Chemical shifts from
Page 401 and 402: 400 Table 5.3 Scandium, yttrium, la
Page 403 and 404: 402 Table 5.3 (continued) Metal Oxo
Page 407 and 408: 406 Table 5.4 Titanium and zirconiu
Page 421 and 422: 420 Table 5.6 Chromium sub-group me
Page 423: 422 Table 5.6 (continued) Metal Oxo
Page 445 and 446: 1 INTRODUCTION 6 Metal Aryloxides T
Page 447 and 448: Metal Aryloxides 447 or both of the
Page 449 and 450: R1 OH O R2 R3NH2 −H2O Scheme 6.3
Page 451 and 452: Cl S N N OH O Cl Me 3C NH HN OH HO
Page 453 and 454: N OH N OH Me 3C Me3C HO HO N N OH H
Page 455 and 456: Metal Aryloxides 455 2Ln C 3Hg⊲C6
Page 457 and 458: Metal Aryloxides 457 Mixed halo, ar
Page 459 and 460: product metal aryloxide 1e,1f (Eqs
Page 461 and 462: Metal Aryloxides 461 Eqs 6.39 and 6
Page 463 and 464: O Mg Mg OAr O Metal Aryloxides 463
Page 465 and 466: 3.7 From Metal Hydrides Metal Arylo
Page 467 and 468: Metal Aryloxides 467 Two other impo
Page 469 and 470: Metal Aryloxides 469 Table 6.1 Meta
Page 471 and 472: Table 6.3 W-OAr distances for vario
Page 473 and 474: 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.
Page 655 and 656:
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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