2 Homometallic Alkoxides

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neodymium pentanuclear complex 403 neopentylidene 678 neopentyloxides 56, 428 neptunium see also actinide metals; plutonium; thorium; uranium neptunium methoxide 29 New perspectives in the tailoring of the heterometallic alkoxide derivatives 202 nickel 75 nickel alkoxides 18, 46, 68, 110, 192, 209, 324–326, 362–363 nickel antimony heterometallic compound, octanuclear 432 nickel aryloxides 484, 620–621, 626 nickel bromide methoxide 100 nickel chloride methoxide 100 nickel dichloride 96 nickel dimethoxide 96, 98, 136 nickel metallacycles 464 nickel methoxide 75, 100, 135 nickel monochloride monomethoxide 96 nickel oxo-alkoxides 432, 433–434 nickel(II) tert-butoxide 110 niobate alkoxides 192 niobium 26, 124, 125, 126, 186, 187, 275, 334, 477, 478, 480, 574, 611 alkylation of chloride aryloxides 574 bimetallic derivatives 200 distorted octahedral 353 infrared spectra 73 octahedral 418 niobium alkoxides 32, 66, 67, 85, 87, 102, 114, 132, 281, 385 alkylation of 141 boiling points of 67 heterometallic 362–363 homoleptic 275 molecular complexity of 67 preparation of 37 niobium aryloxides 563, 612 niobium(V) cadium mixed ligand complex, trinuclear 357 niobium(IV) dichloride dimethoxide complex 275 niobium N,N-diethylaminooxide derivatives 126 niobium heterometallic oxo-alkoxide anions 418 niobium isopropoxide 67, 85, 87 niobium lead oxo-ethoxide, decanuclear 418 niobium oxo-alkoxides 384, 417–419 niobium(V) oxo-ethoxide, octanuclear 417 niobium penta-alkoxides 26, 39, 87, 135 niobium pentaethoxide 36, 121 niobium pentaisopropoxide 87, 211 niobium pentakis(trimethylsiloxide) 112 niobium pentamethoxides 56, 87, 275 Index 697 niobium tert-butoxides 87 niobium/tantalum bonds 473 niobotungstate anions 393 nitric oxide 151–152, 154, 283 nitriles 154, 611 2-nitro-phenoxides 447 NMR (nuclear magnetic resonance) spectroscopy 72, 77, 391–393 nona-alkoxodimetallates 213, 215 nona-alkoxostannates 213 nona-dimetallate(IV) ligands, bonding modes 216–220 nonamacrocyclic tetra-aryloxide 452 nontransition metals 335 heterometallic complexes 353 norbornadienes 678 norbornenes 574, 678, 679 O 1,7-octadiene 563 octaethylporphyrin (oep) 274 octahedral, distorted 298 octamolybdates 426 olefins see alkenes oligomerization 29, 52, 138, 391, 474, 509, 672 oligomers 29, 509, 678 Oppenauer oxidation reactions 108, 141, 147–148 organoheterometallic alkoxide chemistry 140 organoimide alkoxides, binuclear 292 organometallic alkoxides 4, 364, 367 organometallics 4, 464 organoytterbium complex, dinuclear 263 osmium 432 osmium(IV), Schiff base alkoxo complex 321 osmium alkoxides 321, 322 osmium aryloxides 611, 616 oxa-aza-metallacycle 561 2-oxa-titanacyclopent-4-ene rings 611 oxidation reactions 45–46, 141–148 oxidative addition reactions 149–150, 478 oxides 5, 31 heterometal 674 oximate derivatives, homoleptic 125 oximes 106, 125, 127 oximes and N,N-diethylhydroxylamine, reactions of 125–127 oxine (8-hydroxyquinoline) 445 oxiranes, ring-opening polymerization 679 oxo vanadatrane 390 oxo vanadium complexes 412
698 Index oxo-alkoxides 384, 385, 386, 393, 398–399, 405–412, 413-415, 428–432 alkali-metal containing 396–398 bimetallic 679 chemical reactivity of 390–391 chromium sub-group metal-containing 419, 420–424 formation by nonhydrolytic reactions of alkoxides 385–388 heterometallic 385 hexanuclear mixed ligand 409 isolation of 17 structures of 432 oxoniobium trialkoxides 396 oxovanadatrane molecules 412 oxovanadium 1,2-diolates 125 oxovanadium alkoxides 87 oxovanadium trialkoxides 88 oxovanadium trimethoxide 87 P p-block metal alkoxides 24, 31, 32, 242–250 p-block metals 17, 20, 28, 116 paints, heat-resisting 680 palladium(II) 127 palladium, cyclopalladated compounds 464 palladium alkoxides 27, 325, 326 palladium aryloxides, simple 622–624 palmitic acid 123 paramagnetism 93, 472, 613 penta-alkoxides 39 penta-alkoxometallates 213, 216, 219 pentagonal bipyramidal geometry 611 pentene 137, 613, 614 phenol 446, 483 phenol-alcohol exchange reactions 111 phenolic reagents 445, 462, 465 phenols 445, 467 arylation of 650 pi-binding of 467 ortho-alkylation by alkenes 633 phenoxides 111, 447, 464, 466, 478, 483 pi-binding 467 2,6-disubstituted 560 nucleus 445 ring 467, 614 phenylacetylene 153 phenylisocyanate 135, 285 phenylmercury methoxide 136 phosphine 139, 296, 460, 574, 613, 631 phosphines, aryl-phosphines 611 phosphorus bridges 296 phosphorus chloride 20 phthalocyanines, synthesis of 679 picric acid (2,4,6-trinitrophenol) 455 piezo-electric materials 671, 674 pinacol 282 pinacolate (2,3-dimethylbutane-2,3-diolate) 271, 293 pivaldehyde 678 platinum, planar Pt(II) complexes 326 platinum alkoxides 27, 325, 326 platinum alkyl-alkoxide complex 137 platinum aryloxides, simple 625 platinum dimethoxides 137 platinum group metal alkoxides 3, 27 plutonium, synthesis of tetra-alkoxides 23 plutonium see also actinide metals; neptunium; thorium; uranium polymerization 52, 108, 614 polymers 29 diene 679 isotactic 509 polymetallic alkoxides 183 Polymetallic <strong>Alkoxides</strong>-Precursors for Ceramics 183 polymethacrylonitrile 675 polymethylmethacrylate 675 polynorbornene 574 polyvanadates, quaternary ammonium salts 389 porphyrin compounds, aryloxide chemistry of 616 potassium 337–338 see also alkali metals; caesium; lithium; rubidium; sodium potassium alkoxide-crown ether complex 679 potassium alkoxides 28, 337 potassium aluminium isopropoxide isopropanolate 337 potassium amides 39 potassium aryloxides 515 potassium hydroxide 31 potassium isopropoxide 24 potassium methoxide 234 potassium perfluoro tert-butoxides 57 potassium phenoxide 509 potassium phenylsiloxo complexes 234 potassium tert-butoxide derivatives 58 potassium tin(II) triphenylsiloxide, binuclear 337 potassium trifluoromethoxides 58 praseodymium 107, 261–262, 353, 403 see also lanthanide metals; cerium; dysprosium; erbium; europium; gadolinium; holmium; lutetium; neodymium; samarium praseodymium alkoxides 32 praseodymium(III) complexes 261 protonolysis reactions 462–464, 537 pseudo-octahedral 297
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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
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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
Page 645 and 646: 645 Table 6.49 Gallium aryloxides B
Page 647 and 648: 647 Table 6.50 Indium aryloxides Bo
Page 649 and 650: Metal Aryloxides 649 Table 6.53 Tin
Page 651 and 652: 651 Table 6.56 Bismuth aryloxides B
Page 653 and 654: REFERENCES Metal Aryloxides 653 1.
Page 655 and 656: Metal Aryloxides 655 56. Y. Nakayam
Page 657 and 658: Metal Aryloxides 657 123. T.W. Coff
Page 659 and 660: Metal Aryloxides 659 202. A. Bell,
Page 661 and 662: Metal Aryloxides 661 268. K. Ishiha
Page 663 and 664: Metal Aryloxides 663 341. B.S. Kali
Page 665 and 666: Metal Aryloxides 665 405. P.N. Rile
Page 667 and 668: Metal Aryloxides 667 483. Y. Hayash
Page 669 and 670: Metal Aryloxides 669 561. A.P. Shre
Page 671 and 672: 672 Alkoxo and Aryloxo Derivatives
Page 687 and 688: 688 Index alkoxometallate(IV) ligan
Page 689 and 690: 690 Index cerium oxo-isopropoxide 3
Page 691 and 692: 692 Index gas-phase photoelectron s
Page 693 and 694: 694 Index lead tert-butoxide 386 Le
Page 695: 696 Index metal-hydrogen bonds clea
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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