2 Homometallic Alkoxides

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infrared spectroscopy and 137 insoluble 18, 27 interactions between 108, 149 magnetic properties 96 molecular complexities of 55–73, 101 monomeric 27 mononuclear 40 oligomeric 383 oligomerization and volatility of metal 201 physical properties of 51–105 reactions between 186–189 reactions catalysed by 679–680 reactions of soluble 21 reactions with acyl halides 106, 131–133 reactions with bidentate ligands 128 reactions with carboxylic acids 121–123 reactions with dialkanolamines 115 reactions with esters 106 reactions with ethanolamine 114 reactions with hydrogen halides 106 reactions with silanols 112 reactions with silyl esters 106 reactions with unsaturated substrates 106 reactions with water 108, 383 solubility of 3, 18, 35–36, 48 spectral data of diamagnetic 78 spray coating and flash evaporation of 673–674 structures of 51–55, 105 synthesis of 4–51, 43, 106, 186–201 tetraheterometallic 183 transesterification reactions 5, 37–39, 112 triheterometallic 183, 197 trimetallic 183 trinuclear homoleptic 364 volatility of 3, 61, 671, 673 metal alkyls 49 metal alkyls and aryls 462–464 metal amyloxides, molecular complexities of 56 metal aryloxides 1, 445, 459, 464, 483 bonding of 466–478 coordination of 448, 617 cyclometallated 448, 464, 479 homoleptic complexes of 463 mixed alkyl 533, 574 mixed halo 457 normal 509–652 simple 614 special 485–509 survey of 485–652 synthesis of 453–466, 461 terminal M-O-Ar angles 473–477 terminal M-OAr bond distances 468–473 metal aryloxides bonds 467, 482–484 metal bi-naphtholates 501, 505–508 Index 695 metal bi-phenolates 503–504 metal bromides 456 metal catecholates 485 metal chloride alkoxides 99, 132, 195, 1945 metal chlorides 22, 50, 131, 456 alcohoysis reactions of tetravalent 19 reactions with alcohol in base 21 metal dialkoxides 15, 101 metal dialkylamides 39, 40, 41, 460–461 metal ethoxides 75, 106, 132 stretching frequencies 76 metal halide alkoxides 4 metal halides 19, 29, 456–460, 485, 538 direct reactions with alcohols 19–21 reactions with alkali alkoxometallates 190–192 reactions with alkoxides 133, 192 metal hexafluoroisopropoxides 102 metal homoleptic glycolates 123 metal hydrides 48, 465–466 metal hydrides and alkyls, substitution/addition reactions 192 metal 8-hydroxyquinolates 485, 486–500 metal iodides 456 metal isopropoxides 36, 106, 132, 403, 1096 metal methoxides 184 special characteristics of 56–57 synthesis of insoluble 29 metal N,N-diethylhydroxylamines 127 metal oxidation state 77, 467 metal oxides 390, 671–674 reactions with alcohols 389 synthesis of insoluble 28–29 metal oxides by chemical vapour deposition (MOCVD) 671–673 metal oximes 127 metal oxo-alkoxides 1, 4, 102, 383–443 chemistry of 109 mass spectral studies 393 physical properties 391–396 synthetic methods 383–390 metal oxo-chlorides, reactions with alkali alkoxides 388–389 metal oxygen terminal frequencies 392–393 metal salicylaldehydes 485–501 metal salicylates 501, 502 metal siloxides 111, 112 metal tert-butoxides 132 metal tetrachlorides, reactions of 19 metal tetrasiloxides 112 metal-alkyl bonds 462 metal-aryl compounds, oxygenation of 464 metal-aryloxide bonds 445, 448, 460, 475 metal-carbon bonds cleavage reactions 5, 46–47, 48 insertion of aldehydes or ketones 49 insertion of oxygen into 49
696 Index metal-hydrogen bonds cleavage reactions 5, 48 insertion of aldehydes or ketones 49 metal-iodide-isopropoxide complexes, preparation of polyvalent 20 metal-ligand bond lengths 469, 472 metal-metal bonded alkoxides, special reactions of 108, 149–155 metal-metal bonds 39–43, 54 metal-nitrogen bonds, cleavage reactions 48 metal-oxide ceramic materials 185, 197 metal-oxygen bonds 33, 105 metal-oxygen vibrations 391 metalatrane synthesis 271 metallacycles 464, 478 metallacyclopentadiene complex 612 metallacyclopropane 480 metallanorbornadiene 612, 613 metallo-organic compounds 106 metalloenzymes 451 metalloid alkoxides 31, 105 metal(loid) alkoxides 32, 112 metalloid alkoxides, synthesis of 4 metal(loid) halides 21 metalloids 4 oximes 127 metallolactone, formation of 483 metalloproteins 445, 449 metals alkoxides of trivalent 672 anodic dissolution of 4, 18 bivalent 124, 194 electropositive 4, 5, 52, 454 hexavalent 124 organometal hydroxides 31 organometal oxides 31 pentaavalent 124 preparation of bimetallic alkoxides 187–189 reactions with alcohols 5–18 structures of alkoxo compounds 233–333 tetra-alkoxoaluminates of trivalent 210 metals and metalloids, beta-ketoamine derivatives 128 metathesis reactions 24, 457, 509, 615 methanolysis 204 methoxides 18, 25, 28–29, 75, 136, 416, 462, 677 methoxo polyvanadate 390 methoxo titanotungstate anion 411 1,2-methoxyethanol 44 2-methoxyethanol 403, 404 2-methoxyethoxide 18, 25 methyl aluminium oxo-methoxide anion, heptanuclear 436 methyl methacrylate, polymerization of 635 2-methyl-methylenecyclohexane 563 1-methyl-norbornene 614 methylacetoacetate 119, 210 methylberyllium 81 methylimidazole 518, 616, 626 methyllithium 140, 141 methylmagnesium tert-butoxide 81 2-methylpentane-2,4-diol 197 4-methylphenol 479, 616 4-methylphenoxide 466, 472, 484 methylzinc methoxide 60 Michael addition 635 MOCVD (metallo-organic chemical vapour deposition) 3, 197, 516, 674 molecular weight data 1, 52, 120 molybdacyclopentadiene 284 molybdenum 127, 150, 280–289, 290, 613 alkoxo molybdenum compound 280 anodic oxidation 18 dimolybdenum hexa-alkoxides 136, 139, 149, 150 cis-dioxo molybdenum(VI) derivatives 419 molybdenum alkoxides 30, 44, 68, 102, 134, 300–319 dimeric 232 synthesis of 43 molybdenum aryloxides 587–591 molybdenum chloride isopropoxide 287 molybdenum fluoroalkoxides 26 molybdenum hexamethoxide, synthesis of 50 molybdenum neopentylidene complex 679 molybdenum oxo-alkoxides 387, 388, 389, 390, 419–427 molybdenum tetrakis-perfluoro-tert-butoxo compound, monoxo 419 mono-cyclopentadienyl yttrium alkoxo compounds 254 mono-phenoxides, chelating 447–448 monoalkanolamines 113, 114–115, 127 monoalkyltin diisopropoxide monoacetylacetonate 120 monoalkyltin diisopropoxide monobenzoylacetonate 120 monoalkyltin trialkoxides 72 monomethylaluminium 436 mullite 675 N neodymium 60, 107, 262–263 see also cerium; dysprosium; erbium; europium; gadolinium; holmium; lanthanide metals; lutetium; praseodymium; samarium neodymium alkoxides 16, 32, 261 neodymium isopropoxides 60
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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
Page 643 and 644: 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: 694 Index lead tert-butoxide 386 Le
Page 697 and 698: 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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