2 Homometallic Alkoxides

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Index Page numbers in italics refers to illustrations and tables. A acetaldehyde 49, 143, 145 acetone 49, 147, 148, 384, 672, 679 acetonitrile 262, 518 acetyl chloride 133, 501 acetylacetonates 285, 538 acetylacetone 107, 120, 121, 210 acetylenes see alkynes acid anhydrides 5, 30, 121–123 actinide metal alkoxides 8–9, 60, 82–84, 109, 266–268, 269–270 actinide metal aryloxides 457, 533–537 actinide metal halides 19 actinide metal hydrides 51 actinide metals see also neptunium, plutonium, thorium, uranium actinide oxo-alkoxides 400–402, 405 alcohols 5, 31, 43, 106, 189, 271, 467 dihydrox 123 epoxidation of allyli 675–677, 679 exchange reactions 109–110 monodentate 15, 41 alcoholysis 5, 32, 35, 38, 46, 109, 110, 112, 136, 203, 204 aldehydes 137, 142, 153, 635, 679, 680 alkali alkoxometallates 186, 187 alkali metal alkoxides 1, 5, 6, 21, 24, 25, 26, 57–58, 79, 101, 183, 184, 186, 187, 235–236, 334–338, 339–345, 672, 675, 679 structures of 233–234 alkali metal amides 675 alkali metal aryloxides 457, 465, 509–516 alkali metal butoxides, tertiary 221, 232 alkali metal fluoroalkoxides 44, 59 alkali metal halides, insoluble 29 alkali metal isopropoxide 213 alkali metal nonaalkoxodizirconates, synthesis of 213 alkali metal oxo-alkoxides 396–398 alkali metal pentaalkoxometallates 219 alkali metal phenoxides 509 alkali metal tetra-alkoxoaluminates 206 alkali metal trifluoromethoxides 58 alkali metals 4, 28, 52, 502 hexaisopropoxotantalates 211 reactions with alcohols 5–15 alkali metals see also caesium, lithium, potassium, rubidium, sodium alkaline earth metal alkoxides 1, 6–7, 15, 58–60, 80–81, 139, 198, 212, 672 alkaline earth metal aryloxides 19, 516–518 alkaline earth metal chloride-alkoxides 19 alkaline earth metal isopropoxides, reactions of 200 alkaline earth metals 4, 19, 40, 48, 52, 59, 124, 184 homometallic glycolates 198, 199 reactions with alcohols 15–16, 197 alkaline earth metals see also barium, beryllium, calcium, magnesium, strontium alkanolamines 106, 113–117 alkene elimination 15, 385 alkene metathesis 613, 615, 678 alkenes 69, 137, 448, 509, 615, 678 addition of 480 catalytic polymerization of 675 metathesis of 613, 677–680 reactions of dimetal hexa-alkoxides with 152–153 alkoxide acetates, mixed 132 alkoxide derivatives, preparation from metal(loid) hydroxides and oxides 30–32 alkoxide-phenoxide derivatives, isolation of mixed 111 alkoxides see metal alkoxides alkoxo-metal compounds, X-ray crystal structures 229–382
688 Index alkoxometallate(IV) ligands, heterometallic alkoxides and 203, 213–220 alkoxometallates 194, 220 alkoxozinc hydrides 48 alkoxysilane/metal alkoxide mixtures, hydrolyzed 673 alkoxytitanium silsesquioxane 677 alkylalkoxysilanes 36 alkylidene 480, 574, 614, 615, 677 alkylidyne 296, 480, 614 alkylidyne metal complexes 677–678 alkylmagnesium alkoxides, solubility of 60 alkylmagnesium tert-butoxides, NMR spectra of 81 alkylsilicon alkoxides, infrared and Raman spectra 74 alkynes, cyclotrimerization of 562 alkynes (acetylenes) 283, 295, 611, 678 metathesis and polymerization of 677–680 reactions with dimetal hexa-alkoxides 152–153 reactions with tetranuclear alkoxides 154 2-allylphenol 448, 625 aluminates, stability of 212 aluminium 4, 51, 73, 124, 125, 186, 187, 210, 353, 673 bimetallic derivatives 200 dimethylaluminium 436 mononuclear pseudo-tetrahedral complex 243 aluminium alkoxides 17, 32, 37, 56, 69, 70, 71, 74, 88, 130, 132, 143, 145, 147, 242, 244–245, 679 homoleptic 46 reactions with carboxylic acids 106 reactions with ramified alcohols 122 aluminium alkyl substrates 464 aluminium amyloxides, isomeric 56 aluminium aryloxides 6, 473, 631, 633, 635, 636, 637–644 aluminium N,N-diethylaminooxide 126 aluminium ethoxide 33, 74, 103, 143, 144 aluminium hydride 48 aluminium isopropoxide 71, 74, 89, 91, 144, 146, 187, 232 alcoholysis of 33 tetrameric 40, 90, 92, 202, 242 aluminium nitride 680 aluminium oxo-alkoxides 384, 393, 433–434, 435 aluminium oxynitride 680 aluminium phenoxide 633 aluminium sec-butoxide, reaction with palmitic acid 122 aluminium silicates 675 aluminium tert-butoxide 89, 92, 133, 147, 242 aluminium tetraisopropoxo aluminate 242 aluminium trialkoxides 17, 69, 102 aluminium tribenzyloxide 91 aluminium tricarboxylates 106, 121, 122 aluminium trichloride 133 aluminium triethoxide 17, 145 aluminium trifluoroethoxide 436 aluminium triisopropoxide 102, 145 aluminium trimethylsiloxo compounds 242 aluminium tris-beta-diketonates 118 aluminium zirconium oxide 675 amides 43, 193, 485 2-amidophenoxides 449 amines 39, 110, 127, 139, 193, 452 aminoalkoxides 113, 197 ammonia 5, 21, 28, 39, 57 ammonium halides, insoluble 29 ammonium metavanadate 390 antiferromagnetism 99, 274, 280, 330 antimony 119, 124, 125, 126, 186, 636 antimony alkoxides 28, 32, 73, 114, 130, 145, 251 antimony aryloxides 649–650 antimony N,N-diethylaminooxide derivatives 126 antimony pentamethoxide 247 antimony trialkoxides 137 antimony trimethoxide 250 arsenic 125, 126 arsenic alkoxides 28, 31, 73 arsenic N,N-diethylaminooxide derivatives 126 arsenic trialkoxides 137 arsenyl trimethoxide 131 aryloxide ligands 445–453, 466, 467, 468, 478–484, 482, 485, 501, 533, 635 aryloxides see metal aryloxides arylselenato complexes 285 aza-titanacyclopropane 561 azeotropes 34, 35, 37, 389 B barium 16, 238, 346–347, 399, 454, 516 see also alkaline earth metals; beryllium; calcium; magnesium; strontium barium alkoxides 41, 218, 239–240, 348–352, 385 barium aryloxides 519–520 barium copper(I) complex, hexanuclear 347 barium dialkoxides 60, 238 barium dialuminium tetrakis-1,2-ethandiolate 347 barium hexaisopropoxoniobate, bimetallic 192
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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
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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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 685: 686 Alkoxo and Aryloxo Derivatives
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 and 696: 696 Index metal-hydrogen bonds clea
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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