2 Homometallic Alkoxides

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460 Alkoxo and Aryloxo Derivatives of Metals This process can also lead to the formation of metal–aryloxide bonds via activation of pendant methoxy-aryl groups. For example the treatment of [Cp⊲ 5 -C5H4CEt2C6H4OMe-2⊳TiCl2] with LiBr was found to lead to the chelating phenoxide [Cp⊲ 5 -C5H4CEt2C6H4O-2⊳TiCl]. 114 The use of 2,6-dimethoxyphenyl substituents can lead to bulky phosphine ligands. Early work by Shaw et al. showed that ligands such as PBu t 2 fC6H3⊲OMe⊳2-2,6g can generate aryloxy-phosphines with elimination of MeCl at iridium metal centres. 115 This type of reaction is now been extended to a variety of metal systems. 116,117 In some situations the activation by metal centres of the stronger aryl-O bond can occur within aryl-ethers. 118 3.4 From Metal Dialkylamides The homoleptic metal dialkylamides are an important class of compounds in inorganic chemistry. 119 They are typically synthesized by treatment of the corresponding halide with lithium or sodium dialkylamide. Although involving an extra synthetic step, there are numerous examples where metal dialkylamide intermediates are useful in the synthesis of metal aryloxide compounds. The reaction normally involves the simple addition of the parent phenol to the metal dialkylamide in a nonprotic, typically hydrocarbon, solvent (Eqs 6.36, 120 6.37, 121 and 6.38 122 ). Ce[N⊲SiMe3⊳2]3 C 3HOAr ! Ce⊲OAr⊳3 C 3HN⊲SiMe3⊳2 ⊲6.36⊳ Me3C where HOAr = HO X; X = H, Me, CMe3 . Me 3C Me2N Mo Me2N NMe2 NMe2 Mo NMe2 NMe2 H3C where ArOH = HO . H 3C 6ArOH ArO Mo ArO ArO Mo OAr OAr OAr + 6HNMe2 (6.37) [fYb⊲NR2⊳⊲ -NR2⊳g2] C4HOAr ! [fYb⊲OAr⊳⊲ -OAr⊳g2] ⊲6.38⊳ 4HNR2 Bu t where R = SiMe3; OAr = O Me. Bu t The dialkylamine that is produced can be readily removed, leaving the desired product. In some instances, either incomplete substitution can occur (bulky aryloxides,
Metal Aryloxides 461 Eqs 6.39 and 6.40 123 ) or the generated dialkylamine can remain in the metal coordination sphere (Eq. 6.41 124 ) or even deprotonate acidic phenols (Eq. 6.42 125 ). Removal of the bound dialkylamine from adducts of this type can sometimes be difficult. M⊲NMe2⊳4 C 2HOAr ! M⊲OAr⊳2⊲NMe2⊳2 C 2HNMe2 ⊲6.39⊳ Me 3C where M = Ti, Ge, Sn; ArOH = HO . Me2N Mo Me2N NMe2 NMe2 Mo NMe2 NMe2 Ph where HOAr = HO . Ph Me3C 3ArOH ArO Mo Me2N OAr NMe2 Mo OAr NMe2 + 3HNMe2 (6.40) Mo⊲NMe2⊳4 C 4HOAr ! trans-[Mo⊲OAr⊳4⊲HNMe2⊳2] C 2HNMe2 ⊲6.41⊳ where ArOH = HO . Me2N NMe 2 Me 2N W W where ArOH = HO Ph NMe2 NMe2 F F 3.5 From Metal <strong>Alkoxides</strong> F F 10ArOH F . ArO ArO W Me2HN ArO NHMe2 W OAr OAr OAr + 4[NH2Me2][OAr] (6.42) The combination of the greater acidity and the typically lower volatility of phenols over alcohols allows metal alkoxides to be used as precursor for the synthesis of corresponding aryloxide derivatives (Eq. 6.43 126,127 ). Ge⊲OR⊳4 C 4HOPh ! Ge⊲OPh⊳4 C 4HOR ⊲6.43⊳
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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
Page 409 and 410: 408 Alkoxo and Aryloxo Derivatives
Page 415 and 416: 414 Table 5.5 (continued) Metal Oxo
Page 421 and 422: 420 Table 5.6 Chromium sub-group me
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: product metal aryloxide 1e,1f (Eqs
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
Page 475 and 476: Zr−O distance (Å) V−O distance
Page 477 and 478: Metal Aryloxides 477 as expected ar
Page 479 and 480: Metal Aryloxides 479 whereas R D Me
Page 481 and 482: 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-
Page 489 and 490: 489 [Tc(O)(OAr)(di-OAr)] 8-quin 2.0
Page 491 and 492: 491 [Ni3⊲OAr⊳6][ClO4].EtOH 8-qu
Page 493 and 494: 493 [Pt(OAr⊳2](tcnq) sq. planar P
Page 495 and 496: 495 [Al(OAr) 3].MeOH 8-quin 1.850 (
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
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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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