2 Homometallic Alkoxides

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Heterometallic <strong>Alkoxides</strong> 227 185. D. Bright, A.J. Kolombos, G.H.W. Milburn, R.S. Nyholm, and M.R. Truter, J. Chem. Soc., Chem. Commun., 49 (1970). 186. B.A. Vaarstra, J.C. Huffman, P.S. Gradeff, L.G. Hubert-Pfalzgraf, J.C. Daran, S. Parraud, K. Yunlu, and K.G. Caulton, Inorg. Chem., 29, 3126 (1990). 187. W.J. Evans, M.A. Greci, M.A. Ansari, and J.W. Ziller, J. Chem. Soc., Dalton Trans., 4503 (1997). 188. R.C. Mehrotra and A. Singh, Polyhedron, 17, 689 (1998). 189. D.C. Bradley, Adv. Chem. Ser., 23, 10 (1959). 190. N.Ya. Turova, V.A. Kuzunov, A.I. Yanovsky, N.G. Bokii, Yu.T. Struchkov, and B.L. Turnopolsky, J. Inorg. Nucl. Chem., 41, 5 (1979). 191. K. Folting, W.E. Streib, K.G. Caulton, O. Poncelet, and L.G. Hubert-Pfalzgraf, Polyhedron, 10, 1639 (1991). 192. R.C. Mehrotra and M.M. Agrawal, J. Chem. Soc., Chem. Commun., 469 (1968). 193. D.C. Bradley, Phil. Trans. Roy. Soc., London, A330, 167 (1990). 194. N.Ya. Turova, E.P. Turevskaya, M.I. Yanovskaya, A.I. Yanovsky, V.G. Kessler, and D.E. Tcheboukov, Polyhedron, 17, 899 (1998). 195. R.C. Mehrotra and R. Bohra, Metal Carboxylates, Academic Press, London (1983). 196. R.C. Mehrotra, D.P. Gaur, and R. Bohra, Metal ˇ-Diketonates and Allied Derivatives, Academic Press, London (1978). 197. R.C. Mehrotra, in Recent Trends in Inorganic Chemistry (A. Chakravorty ed.), 256–275, Indian National Science Academy Publications (1986). 198. R.C. Mehrotra, in Sol–Gel Science & Technology (M.A. Aegerter, M. Jafelicci Jr, D.F. Souza, and E.D. Zanotto, eds), 17–60, World Scientific, Singapore (1989). 199. L.C. Francis, V.J. Ola, and D.A. Payne, J. Mater. Sci., 25, 5007 (1990). 200. E.P. Turevskaya, M.I. Yanovskaya, V.K. Lymar, and N.Ya. Turova, Russ. J. Inorg. Chem., 38, 563 (1993). 201. J. Rai and R.C. Mehrotra, J. Non-Cryst. Solids, 134, 23 (1991). 202. J. Rai and R.C. Mehrotra, Main Group Met. Chem., 15, 209 (1992). 203. J. Rai and R.C. Mehrotra, J. Non-Cryst. Solids, 152, 119 (1993). 204. R.C. Mehrotra, in Facets of Coordination Chemistry (B.V. Agarwal and K.N. Munshi, eds), World Scientific, Singapore (1993). 205. N.C. Jain, A.K. Rai, and R.C. Mehrotra, Indian J. Chem., 14A, 256 (1976). 206. J.A. Meese-Markscheffel, R.E. Cramer, and J.W. Gilje, Polyhedron, 13, 1045 (1994). 207. R.C. Mehrotra and M. Aggrawal, Polyhedron, 4, 1141 (1985). 208. G. Garg, R.K. Dubey, A. Singh, and R.C. Mehrotra, Polyhedron, 10, 1733 (1991). 209. R. Jain, A.K. Rai, and R.C. Mehrotra, Polyhedron, 5, 1017 (1986). 210. R. Jain, A.K. Rai, and R.C. Mehrotra, Inorg. Chim. Acta, 126, 99 (1987). 211. R.C. Mehrotra, M.M. Agrawal, and P.N. Kapoor, J. Chem. Soc., A, 2673 (1968). 212. E.P. Turevskaya, N.Ya. Turova, A.V. Koraler, A.I. Yanovsky, and Yu.T. Struchkov, Polyhedron, 14, 1531 (1995). 213. D. Eichorst, D.A. Payne, S.R. Wilson, and K.E. Hasord, Inorg. Chem., 29, 1458 (1990). 214. D.E. Tchebukov, N.Ya. Turova, A.V. Korolev, and A.I. Belokon, Russ. J. Inorg. Chem., 42, 10 (1997). 215. S. Mathur, A. Singh, and R.C. Mehrotra, Polyhedron, 12, 1073 (1993). 216. D.C. Bradley, E.V. Caldwell, and W. Wardlaw, J. Chem Soc. A, 4775 (1957). 217. F.A. Cotton, D.O. Marler, and W. Schwotzer, Inorg. Chem., 23, 4211 (1984). 218. W.J. Evans, T.J. Deming, J.M. Olofson, and Z.W. Ziller, Inorg. Chem., 28, 4027 (1989). 219. D.L. Clark and J.G. Watkin, Inorg. Chem., 32, 1766 (1993). 220. G. Garg, A. Singh, and R.C. Mehrotra, Polyhedron, 12, 1399 (1993). 221. S. Sogani, A. Singh, and R.C. Mehrotra, Polyhedron, 14, 621 (1995). 222. U.M. Tripathi, A. Singh, and R.C. Mehrotra, Polyhedron, 12, 1947 (1993). 223. I. Baxter, S.R. Drake, M.B. Hursthouse, K.M. Abdul Malik, D.M.P. Mingos, J.C. Plakatouras, and D.J. Otway, Polyhedron, 17, 625 (1998). 224. S. Sogani, A. Singh, and R.C. Mehrotra, Main Group Met. Chem., 13, 375 (1990). 225. T.J. Boyle, D.C. Bradley, M.J. Hampden-Smith, A. Patel, and J.W. Ziller, Inorg. Chem., 34, 5893 (1995). 226. D.J. Teff, C.D. Miner, D.V. Baxter, and K.G. Caulton, Inorg. Chem., 37, 2547 (1998).
228 Alkoxo and Aryloxo Derivatives of Metals 227. J.A. Samuels, B. Labkorsky, W.E. Streib, K. Folting, J.C. Huffman, J.W. Zwanziger, and K.G. Caulton, J. Am. Chem. Soc., 115, 5093 (1993). 228. S.N. Putlin, E.V. Antipov, O. Chaissen, and M. Mariezo, Nature, 363, 56 (1993). 229. T.A. Wark, E.A. Gulliver, and M.J. Hampden-Smith, Inorg. Chem., 29, 4360 (1990). 230. V.W. Day, T.A. Eberspacher, J. Haq, W.G. Klemperer, and B. Zhong, Inorg. Chem., 34, 3549 (1995). 231. M. Veith, Phosphorus, Sulphur, Silicon, 11, 195 (1989). 232. T. Athar, R. Bohra, and R.C. Mehrotra, Indian J. Chem., 28A, 302 (1989). 233. B. Barup, W.E. Streib, and K.G. Caulton, Chem. Ber., 129, 1003 (1996). 234. R.C. Mehrotra, Chemtracts, 7, 182 (1995). 235. M. Veith, S. Mathur, and V. Huch, Phosphorus, Sulphur, Silicon, 124–125, 493 (1997). 236. M. Veith, S. Mathur, C. Mathur, and V. Huch, Organometallics, 17, 1044 (1998). 237. W. Clegg, A.M. Drummond, S.T. Liddle, R.E. Mulvey, and A. Robertson, J. Chem. Soc., Chem. Commun., 1559 (1999).
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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 173 694. R.C
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Page 179 and 180: Homometallic Alkoxides 177 876. J.
Page 181 and 182: Homometallic Alkoxides 179 966. H.
Page 183 and 184: Homometallic Alkoxides 181 1054. M.
Page 185 and 186: 184 Alkoxo and Aryloxo Derivatives
Page 227: 226 Alkoxo and Aryloxo Derivatives
Page 237 and 238: 236 Table 4.1 (Continued) M-O Bond
Page 245 and 246: 244 Table 4.3 Alkoxides of aluminiu
Page 249 and 250: 248 Table 4.4 Alkoxides of germaniu
Page 257 and 258: 256 Table 4.6 Alkoxides of scandium
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
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278 Table 4.9 (Continued) Bond leng
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280 Alkoxo and Aryloxo Derivatives
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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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304 Table 4.11 (Continued) M-O Bond
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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
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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
Page 591 and 592:
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
Page 603 and 604:
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-
Page 611 and 612:
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
Page 619 and 620:
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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Page 629 and 630:
629 [(RNC) 2Cu⊲ 2-OAr⊳2Cu(CNR)
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Metal Aryloxides 631 The two-coordi
Page 633 and 634:
Table 6.45 (Continued) Metal Arylox
Page 635 and 636:
Table 6.47 Simple aryloxides of mer
Page 637 and 638:
637 Table 6.48 Aluminium aryloxides
Page 639 and 640:
639 [⊲ArO⊳2Al⊲ -OAr⊳2Mg(THF
Page 641 and 642:
641 [Al(OAr) 2⊲i-Bu⊳] trigonal
Page 643 and 644:
643 [Al(OAr)Cl(Me)⊲NH2But⊳] OC6
Page 645 and 646:
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
Page 699 and 700:
700 Index sodium hydroxide 142 sodi
Page 701 and 702:
702 Index titanium dichloride dieth
Page 703:
704 Index X X-ray Absorption Near E
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2 Homometallic Alkoxides

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