2 Homometallic Alkoxides

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534 Table 6.20 Actinide aryloxides Bond length ( ˚A) Bond angle ( Ž ) Compound Aryloxide M–O M–O–Ar Ref. [Th(OAr) 4] tetrahedral Th [⊲pyrazolyl⊳2Th(OAr) 2] 8-coord. Th OC6H3But 2-2,6 2.189 (6) 154 i OC6H5 2.181 (6) 2.172 (6) [Th(OAr) 2⊲CH2-py-6Me⊳2] 6-coord. Th OC6H3But 2-2,6 2.190 (9) 175 iii [Th(OAr) 2⊲CH2SiMe3⊳2] OC6H3But 2-2,6 2.15 (1) 2.13 (1) 162 177 iv [Th3⊲ 3-H⊳2⊲ 2-H⊳4⊲OAr⊳6] triangular cluster, all terminal OAr OC6H3But 2-2,6 2.164 (7) 2.126 (7) 178 168 iv 2.158 (7) 179 2.144 (7) 166 2.139 (7) 178 2.128 (7) 171 [Th(OAr) 4⊲py⊳2].toluene cis py ligands OC6H3Me2-2,6 2.211 (6) 2.188 (6) 169 176 i 2.206 (6) 172 2.183 (6) 176 [⊲ArO⊳⊲H2O⊳6Th⊲ 2- OH2⊳Th(OAr)⊲OH2⊳6]⊲OAr⊳4.20H2O [Cp OC6H2⊲NO2⊳3-2,4,6 2.366 (3) 156 v Ł Th(OAr) 2Br] three-legged piano stool OC6H3But 2-2,6 2.18 (1) 2.139 (8) 162 170 vi 173 169 ii
535 [Cp Ł Th(OAr)⊲CH2SiMe3⊳2] three-legged piano stool OC6H3But 2-2,6, 2.186 (6) 171 vi [Cp Ł Th⊲OC6H3But-CMe2CH2⊲OAr⊳⊲OPPh2⊳] distorted tbp, Cp Ł and cyclometallated O axial OC6H3But 2-2,6 OC6H3But-CMe 2 [fU2⊲OAr⊳3⊲thf⊳g2fU(O) 2⊲thf2g⊲ 2-OAr⊳4⊲ 3-O⊳] tetrameric unit, two U(V) andtwoU(VI) atoms. CH2 OC6H5 2-OC6H5 2.205 (7) 2.192 (6) 2.03 (2) 2.08 (2) 2.12 (2) 2.46 (2), 2.33 (2) 2.40 (2), 2.42 (2) 163 148 174 164 158 vi vii [U(OAr) 4⊲dmpe⊳2] dodecahedron OC6H5 2.16 (1) 2.17 (1) 166 164 viii 2.18 (1) 162 2.18 (1) 167 [U(OAr) 3⊲NEt2⊳] tetrahedral U OC6H3But 2-2,6 2.140 (4) 2.146 (4) 149 163 ix 2.143 (4) 150 [U2⊲O- 6-Ar⊳2⊲OAr⊳4] two 3-coord. U held together by 6-phenoxy interactions OC6H3Pri 2-2,6 O- 6-C6H3Pri 2-2,6 [U(OAr) 4] tetrahedral U OC6H3Bu 2.132 (8) 2.214 (7) 165 157 x t 2-2,6 2.135 (4) 154 i, xi [U(OAr) 3I] tetrahedral U OC6H3But 2-2,6 2.092 (8) 2.102 (8) 170 160 xii 2.114 (11) 170 [U(OAr) 2I2(THF)] tbp, axial THF and OAr OC6H3But 2-2,6 2.080 (8) 2.073 (9) 173 166 xii [(ArO) 3U⊲ 2-S⊳U(OAr) 3].OEt2 distorted, non tetrahedral geometry about U OC6H3But 2-2,6 2.079 (9) 2.125 (8) 172 174 xii 2.119 (6) 172 [Cp Ł 2U(O)(OAr)] OC6H3Pri [U(OAr)fN⊲SiMe3⊳2g3] tetrahedral U 2-2,6 OC6H3Bu 2.135 (5) 170 xiii t 2-2,6 2.145 (8) 159 i [(thf) 4K][U(OAr) 2Cl3] tbp U with trans OAr, infinite chain held together by UCl–K–ClU interactions OC6H3But 2-2,6 2.122 (6) 2.123 (6) 155 153 xiv (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
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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
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-
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Page 491 and 492: 491 [Ni3⊲OAr⊳6][ClO4].EtOH 8-qu
Page 493 and 494: 493 [Pt(OAr⊳2](tcnq) sq. planar P
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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 and 528: 527 [⊲THF⊳Li⊲ 2-OAr⊳2Sm⊲C
Page 529 and 530: 529 [Eu⊲ 2-OAr⊳4⊲OAr⊳2⊲ 3
Page 531 and 532: 531 [Yb(OAr) 3⊲THF⊳2].THF squar
Page 533: Metal Aryloxides 533 carbon atoms a
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
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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
Page 579 and 580: 579 [Ta(OAr) 2Cl2⊲CH2C6H5⊳] tbp
Page 581 and 582: 581 [Ta(OAr) 2Cl⊲ 6-C6Me6⊳] OC6
Page 583 and 584: 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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