2 Homometallic Alkoxides

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X-Ray Crystal Structures of Alkoxo Metal Compounds 381 D.V. Berdyev, N.Ya. Turova, and I.M. Yanovskaya, Russ. J. Inorg. Chem., 40, 1527 (1995). 495. M. Veith, S. Mathur, and V. Huch, J. Am. Chem. Soc., 118, 903 (1996); Inorg. Chem., 35, 7295 (1996). 496. S. Boulmaaz, R. Papiernik, L.G. Hubert-Pfalzgraf, and J.-C. Daran, Eur. J. Solid State Inorg. Chem., 30, 583 (1993). 497. E.P. Turevskaya, N.Ya. Turova, A.V. Korolev, A.I. Yanovsky, and Yu.T. Struchkov, Polyhedron, 14, 1531 (1995). 498. A.P. Purdy and C.F. George, Inorg. Chem., 30, 1969 (1991). 499. N.N. Sauer, E. Garcia, K.V. Salazar, R.R. Ryan, and J.A. Martin, J. Am. Chem. Soc., 112, 1524 (1990). 500. W. Bidell, V. Shklover, and H. Berke, Inorg. Chem., 31, 5561 (1992). 501. C.P. Love, C.C. Torardi, and C.J. Page, Inorg. Chem., 31, 1784 (1992). 502. F. Labrize, L.G. Hubert-Pfalzgraf, J. Vaissermann, and C.B. Knobler, Polyhedron, 15, 577 (1996). 503. M.C. Cruickshank and L.S. Dent Glasser, Acta Crystallogr., C41, 1014 (1985). 504. W. Bidell, J. Döring, H.W. Bosch, H.-U. Hund, E. Plappert, and H. Berke, Inorg. Chem., 32, 502 (1993). 505. W.J. Evans, T.J. Boyle, and J.W. Ziller, J. Am. Chem. Soc., 115, 5084 (1993). 506. V.G. Kessler, L.G. Hubert-Pfalzgraf, S. Halut and J.-C. Daran, J. Chem. Soc., Chem. Commun., 705 (1994). 507. U.M. Tripathi, A. Singh, R.C. Mehrotra, S.C. Goel, M.Y. Chiang, and W.E. Buhro, J. Chem. Soc., Chem. Commun., 152 (1992). 508. L.M. Slaughter and P.T. Wolczanski, Chem. Commun., 2109 (1997). 509. M. Veith, S. Mathur, and V. Huch, Chem. Commun., 2197 (1997). 510. R. Papiernik, L.G. Hubert-Pfalzgraf, M. Veith, and V. Huch, Chem. Ber./Recueil, 130, 1361 (1997). 511. R. Schmid, A. Mosset, and J. Galy, Acta Crystallogr., C47, 750 (1991). 512. B.A. Vaarstra, J.A. Samuels, E.H. Barash, J.D. Martin, W.E. Streib, C. Gasser, and K.G. Caulton, J. Organomet. Chem., 449, 191 (1993). 513. S. Sogani, A. Singh, R. Bohra, R.C. Mehrotra, and M. Nottemeyer, J. Chem. Soc., Chem. Commun., 738 (1991). 514. D.J. Teff, J.C. Huffman, and K.G. Caulton, Inorg. Chem., 35, 2981 (1996). 515. J.A. Samuels, J.W. Zwanziger, E.B. Lobkovsky, and K.G. Caulton, Inorg. Chem., 31, 4046 (1992). 516. E.P. Turevskaya, D.V. Berdyev, N.Ya. Turova, Z.A. Starikova, A.I. Yanovsky, Yu.T. Struchkov, and A.I. Belokon, Polyhedron, 16, 663 (1997). 517. S. Boulmaaz, R. Papiernik, and L.G. Hubert-Pfalzgraf, Chem. Mater., 3, 779 (1991). 518. M.H. Chisholm, J.C. Huffman, and J.J. Koh, Polyhedron, 8, 127 (1989). 519. S.L. Latesky and J.P. Selegue, J. Am. Chem. Soc., 109, 4731 (1987). 520. M.H. Chisholm, V.J. Johnston, O. Eisenstein, and W.E. Streib, Angew. Chem. Int. Ed. Engl., 31, 896 (1992). 521. R.J. Blau, M.H. Chisholm, K. Folting, and R.J. Wang, J. Chem. Soc., Chem. Commun., 1582 (1985); J. Am. Chem. Soc., 109, 4552 (1987). 522. M. Veith, C. Mathur, S. Mathur, and V. Huch, Organometallics, 16, 1292 (1997). 523. M. Veith, D. Käfer, J. Koch, P. May, L. Stahl, and V. Huch, Chem. Ber., 125, 1033 (1992). 524. M. Veith, S. Weidner, K. Kunze, D. Käfer, J. Hans, and V. Huch, Coord. Chem. Rev., 137, 297 (1994). 525. M. Veith, S. Mathur, and V. Huch, J. Chem. Soc., Dalton Trans., 2485 (1996). 526. O.Yu. Vassilyeva, L.A. Kovbasyuk, V.N. Kokozay, B.W. Skelton, and W. Linert, Polyhedron, 17, 85 (1998). 527. L.F. Francis, D.A. Payne, and S.R. Wilson, Chem. Mater., 2, 645 (1990). 528. M. Veith and R. Rösler, Angew. Chem. Int. Ed. Engl., 21, 858 (1982).
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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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Page 331 and 332: 330 Alkoxo and Aryloxo Derivatives
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 381: 380 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
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434 Table 5.9 (continued) Metal Oxo
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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
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
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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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