2 Homometallic Alkoxides

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pseudo-square pyramidal configuration 299 pseudo-tetrahedral 336 pseudo-trigonal bipyramidal complexes 357, 437, 678 pyridine 5, 110, 138, 266, 275, 386, 387, 561, 612, 613, 615, 616 pyridine N-oxide 537 pyroelectric materials 674 Q quinol 485 quinoline 447 quinone 286 quinuclidine 153, 267, 432, 678 R Raman spectra 391 reactions, insertion 134–138 reflectance 93–96 rhenium 615 alkylidyne complexes 678 dinuclear organorhenium alkoxo complexes 320 heteroleptic chloride tert-butoxide of 27 rhenium alkoxides 320–321, 322 rhenium aryloxides 462, 603–604, 615 rhenium hexamethoxide, synthesis of 50 rhenium oxo-alkoxides 430 rhenium(VI) oxo-methoxide, binuclear 430 rhenium pentamethoxide, homoleptic 320 rhenium-oxo groups 615 rhodium alkoxides 46, 324 rhodium aryloxides, simple 617 rhodium complexes 484 ring-opening metathesis polymerization (ROMP) 79, 614, 678, 679 rubidium see also alkali metals; caesium; lithium; potassium; sodium rubidium aryloxides 515 rubidium methoxide 234 rubidium phenoxide 509 rubidium tert-butoxide derivatives 58 rubidium trifluoromethoxides 58 ruthenium 479 ruthenium alkoxides 322 ruthenium aryloxides 608–610, 616 S s-block metals 5–16, 24–26, 116 alkoxides of 31, 32 electropositive 4 salicylaldehyde 127, 146, 147, 450, 455, 485 Index 699 salicylaldimine 445, 475 samarium 148, 263 see also cerium; dysprosium; erbium; europium; gadolinium; holmium; lanthanide metals; lutetium; neodymium; praseodymium; samarium samarium alkoxides 32, 148, 212 samarium isopropoxide 60 scandium 250, 385, 435 scandium alkoxides 7, 16, 22, 41, 60, 250–252, 256–257 scandium oxo-alkoxides 400–402 scandium oxo-isopropoxides 385 Schiff bases 106, 127, 128, 129, 680 sebacic acid, esterification of 679 selenium 124 selenium alkoxides 73 Siemens Molecular Analysis Research Tool Charge Coupled Device (SMART CCD) 409 silanols 37, 111–112 silicon 124, 125 silicon alkoxides 3, 31, 50, 55, 72, 74, 115, 130, 132 silicon carbide 680 silicon chloride 20 silicon dichloride diethoxide 50 silicon ethoxide 18, 121 silicon monochloride triethoxide 50 silicon nitride 680 silicon tetra-alkoxides 74 silicon tetrachloride 20 silicon tetraethoxide 50, 72 silicon tetrahalides 130 silicon tetraphenoxide 72 siloxane 3 silver alkoxides 327, 331 silver aryloxides 630, 631 silver nanoclusters 679 silyl acetate 37 silyl esters 112 silyl ketene acetals 680 single electron transfer (SET) mechanism 146 sodium 36, 336–337 see also alkali metals; caesium; lithium; potassium; rubidium sodium alkoxides 23, 28, 31, 142, 145, 336, 679 sodium aluminates 675 sodium amalgam 480, 562, 611 sodium aryloxides 509, 513–514 sodium cerium(IV) tert-butoxide 336 sodium chromium(II) bis-disiloxanediolate 337 sodium dialkylamide 460 sodium ethoxide 45, 57, 142, 143
700 Index sodium hydroxide 142 sodium isopropoxide 24, 57, 389 sodium methoxide 57, 234, 389 sodium perfluoro tert-butoxide 57, 58 sodium tert-butoxide 24, 57, 234 sodium tetraiospropoxaluminate 190 sodium thorium(IV) complex 336 sodium tin(II) tert-butoxide 337 sodium titanium(IV) isopropoxide 336 sodium triphenylsiloxide 234 sodium zirconium oxo-ethoxide 397 sodium zirconium silicon phosphorus oxide 675 sol-gel process 1, 3, 109, 184, 185, 187, 197, 205, 383, 390, 516, 538, 671, 673, 674 spiked-triangular arrangement 299 square pyramidal structure 403 stannylene aryloxides 636 steric effects 230, 384, 409 strontium 338, 346, 516 triphenylsiloxide 238 strontium see also alkaline earth metals; barium; beryllium; calcium; magnesium strontium alkoxides 238, 338–346, 348–352 strontium aryloxides 518 strontium dialkoxides 60, 238 styrene 562, 574, 675 substitution reactions, partial 24, 462 succinic acid, esterification of 679 sulfinyl bridging group 450 sulfur, sulfoxidation of organosulfur compounds 677 sulfur bridging group 450 sulfur dioxide, insertion of 484 sulphuric acid 36 Suzuki coupling 446 synthons 106, 108 T tantalacyclobutane 574 tantalacyclopentadiene 611, 612 tantalate alkoxides 192 tantalcyclopropene 611 tantalum 26, 121, 124, 125, 126, 186, 187, 385, 418, 478, 480, 611 alkylation of chloride aryloxides 574 organotantalum alkoxo compounds 280 tantalum alkoxides 32, 66, 67, 85, 87, 114, 132, 280, 281 alkylation of 141 hydrolysis of 384 infrared spectra 73 preparation of 37 tantalum alkylidene 481 tantalum aryloxides 563, 575–583, 612 tantalum N,N-diethylaminooxide derivatives 126 tantalum distorted octahedral coordination 419 tantalum ethoxide 18 tantalum heterometallic oxo-isopropoxides, hexanuclear 419 tantalum isopropoxide 67, 85, 87 tantalum oxo-alkoxides 384, 418 tantalum penta-alkoxides 26, 39, 87, 102, 135 tantalum pentaethoxides 121 tantalum pentaisopropoxide 36, 85, 86, 211 tantalum pentakis(trimethylsiloxide) 112 tantalum pentamethoxide 36, 56, 85, 87 tantalum tert-butoxides 87 tantalum tribromide 574 technetium alkoxides 320, 322 technetium aryloxides, simple 602 technetium oxo-alkoxides 320, 430 tellurium 124, 450 tellurium alkoxides 28, 32, 73 tellurium ethoxide 73 tellurium isopropoxide 36, 73 tellurium n-butoxide 73 tellurium tetramethoxide 73 terephthalic acid 675 tert-butoxides 40, 44, 58, 60, 65, 150 tert-butyl alcohol 23, 33, 35, 36, 39, 40, 87 tert-butylzinc tert-butoxide, dimeric 81 tetra-alkoxo-metallic derivatives, preparation of 208 tetra-alkoxoaluminate(IV) derivatives 203 tetra-alkoxoaluminates 191, 206–211 N,N,N 0 ,N 0 -tetraethylenediamine (teeda) 110 tetraethyleneglycolate 280 4-tetrafluoroethylene 137 tetraglyme 238 tetragonal bipyramidal configuration 405 tetragonal pyramidal 419 tetrahydrofuran (THF) 15, 48, 141, 253, 390, 454, 516 tetraisopropoxoaluminates 184, 191, 192 tetrametallic alkoxides 185, 195 tetramethoxysilane 31 tetraphenyl disiloxanediolate 238 tetraphenyl siloxanediolate 334 2,3,5,6-tetraphenylphenoxide 613 tetraphenylporphinato aluminium phenoxide 635 thallium 17 thallium alkoxides 23, 31, 92, 232, 244–245, 364, 365–366 thallium aryloxides 645–646 thallium calcium barium copper oxide 675
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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
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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 and 696: 696 Index metal-hydrogen bonds clea
Page 697: 698 Index oxo-alkoxides 384, 385, 3
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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