2 Homometallic Alkoxides

More documents

Recommendations

Info

235 Table 4.1 Alkali metal alkoxides Metal M–O Bond lengths ( ˚A) Bond angles ( Ž ) Compound coordination Terminal Bridging MOC � Reference [LiOMe]1 4 – 1.95 114.5 23 [Li⊲ 3-OCMe2Ph⊳]6 3 – 1.874–1.979 (3) 115.9–139.9 24 (av. 1.915) (av. 124.0) [Li⊲ -OCBu t 3⊳]2 [Lif -OB[CH⊲SiMe3⊳2]2g2]2 [LifOB[CH⊲SiMe3⊳2]2g⊲Me2NC2H4NMe2⊳] [Li⊲ -OCBu 2 2 3 – – 1.667 (15) 1.75 (8) 1.78 (2) – – – – 25 25 25 t CH2PMe2⊳]2 [Li⊲ -OCBu 3 1.78 (1) – – 26 t CH2PPh2⊳]2 [Li⊲ -OCBu 3 1.792 (9) – – 26 t ⊳3⊲thf⊳]2 [Lif -OB⊲Mes⊳2g⊲thf⊳]2 [Li⊲ 3-N -methylpseudoephedrate⊳]2 3 3 3 – – – 1.84 (1) 1.849 (7) 1.870–1.985 (13) (av. 1.929) – – – 27 28 29 [Li⊲ -OSiPh3⊳⊲MeOC2H4OMe⊳]2 3 – 1.881–1.910 (9) 133.0–143.5 30 (av. 1.895) (av. 136.9) [f⊲Ph2SiOLi⊳2O⊲thf⊳g2⊲DABCO⊳2] 3 – 1.803, 1.877 (10) – 31 [f⊲Ph2SiOLi⊳2O⊲thf⊳g2⊲DABCO⊳2] [f⊲Ph2SiOLi⊳2O⊲thf⊳g2⊲4,4 4 – 1.889, 2.014 (10) – 31 0-bipy⊳2] 4 – 1.983 (8) – 31 [LiOCH(C6H4OMe⊳NMeC2H4NMe2]4 4 – 1.852–1.909 (8) – 32 [NaOMe]1 ⊲NaOBu 4 – 2.32 (1) 110.6 33 t⊳6 4 – 2.14–2.32 (3) (av. 2.24) – 34 (continued overleaf )
236 Table 4.1 (Continued) M–O Bond lengths ( ˚A) Metal Bond angles ( Ž ) Compound coordination Terminal Bridging � MOC Reference ⊲NaOBut⊳9 4 – 2.15–2.39 (3) (av. 2.25) – 34 [Na4⊲OSiPh3⊳4⊲H2O⊳3] 3 and 4 – 2.256–2.311 (9) (av. 2.284) – 35 [KOMe]1 5 – 2.60, 2.80 – 36 [RbOMe]1 5 – 2.72, 2.95 – 36 [CsOMe]1 5 – 2.93, 3.14 – 36 [KOBut ]4 3 – 2.56 (2) – 37 [KOBut ]4 3 – 2.623 (1) 125.4 39 [RbOBut ]4 3 – 2.757 (4) 124.6 39 [KOSiMe3]4 3 – 2.61 (4) 123 38 [RbOSiMe3]4 3 – 2.74 (6) 123 38 [KOBut .ButOH] 4 – 2.620, 2.737 (2) – 39 [RbOBut .ButOH] 4 – 2.767 (3), 2.869 (3) – 39 [K⊲18-crown-6⊳⊲OSiPh3⊳]2 8 – 2.625 (2) – 30 [K8⊲OSiPh3⊳8⊲MeOC2H4OMe⊳3] 3, 4, 5 – 2.592 (3)–2.757 (3) (av. 2.662) – 30 [KOSiPh2(OSiPh2)OSiPh2OH]2 3 – 2.681 (4), 2.812 (4) 134.4, 118.1 40
Page 1 and 2:
Alkoxo and Aryloxo Derivatives of M
Page 3 and 4:
1 Introduction In 1978 the book ent
Page 5 and 6:
1 INTRODUCTION 2 Homometallic Alkox
Page 7 and 8:
Homometallic Alkoxides 5 to complet
Page 9 and 10:
Table 2.1 (Continued) Homometallic
Page 11 and 12:
Page 13 and 14:
Page 15 and 16:
Page 17 and 18:
Homometallic Alkoxides 15 reactivit
Page 19 and 20:
Homometallic Alkoxides 17 By contra
Page 21 and 22:
Homometallic Alkoxides 19 2.3 React
Page 23 and 24:
Homometallic Alkoxides 21 has been
Page 25 and 26:
Homometallic Alkoxides 23 obtain on
Page 27 and 28:
y Evans and co-workers: 160,161 Hom
Page 29 and 30:
Homometallic Alkoxides 27 The heter
Page 31 and 32:
Homometallic Alkoxides 29 not conve
Page 33 and 34:
Homometallic Alkoxides 31 In view o
Page 35 and 36:
2.7.2 Steric Factors Homometallic A
Page 37 and 38:
Homometallic Alkoxides 35 (b) When
Page 39 and 40:
Homometallic Alkoxides 37 2.8 Trans
Page 41 and 42:
Homometallic Alkoxides 39 with orga
Page 43 and 44:
2.9.1.1 Alkoxides of Be, Mg, Ca, Sr
Page 45 and 46:
MfN⊲SiMe3⊳2g2thfx C2HOR, Cpy !C
Page 47 and 48:
Homometallic Alkoxides 45 2.10 Misc
Page 49 and 50:
Zr⊲CH2Bu t ⊳4 C 4RfOH benzene !
Page 51 and 52:
2.10.5 By Insertion of Oxygen into
Page 53 and 54:
Homometallic Alkoxides 51 First hom
Page 55 and 56:
O M R M OR M OR RO M (M = Tl; R = M
Page 57 and 58:
Homometallic Alkoxides 55 3. Nuclea
Page 59 and 60:
Homometallic Alkoxides 57 explain t
Page 61 and 62:
Decomposition (%) 100 80 60 40 20 0
Page 63 and 64:
Table 2.6 Volatilities of tetravale
Page 65 and 66:
Homometallic Alkoxides 63 deduced t
Page 67 and 68:
Table 2.10 Vapour pressure of Ti, Z
Page 69 and 70:
Homometallic Alkoxides 67 Table 2.1
Page 71 and 72:
3.2.10 Alkoxides of Later 3d Metals
Page 73 and 74:
Homometallic Alkoxides 71 Table 2.1
Page 75 and 76:
Homometallic Alkoxides 73 affected
Page 77 and 78:
Homometallic Alkoxides 75 the range
Page 79 and 80:
Homometallic Alkoxides 77 several c
Page 81 and 82:
Page 83 and 84:
Homometallic Alkoxides 81 In toluen
Page 85 and 86:
Bu t O Bu t O Bu t O Th O O Bu O t
Page 87 and 88:
Homometallic Alkoxides 85 1H NMR st
Page 89 and 90:
Homometallic Alkoxides 87 septet wa
Page 91 and 92:
Homometallic Alkoxides 89 experimen
Page 93 and 94:
Table 2.21 1 H NMR spectra of Al4(O
Page 95 and 96:
Homometallic Alkoxides 93 3.5 Elect
Page 97 and 98:
Homometallic Alkoxides 95 ligand fi
Page 99 and 100:
Homometallic Alkoxides 97 susceptib
Page 101 and 102:
10 −1 /xM 12 10 −200 −100 0 [
Page 103 and 104:
Homometallic Alkoxides 101 alkoxide
Page 105 and 106:
Homometallic Alkoxides 103 fragment
Page 107 and 108:
Homometallic Alkoxides 105 The mass
Page 109 and 110:
Homometallic Alkoxides 107 [Al⊲OP
Page 111 and 112:
Homometallic Alkoxides 109 Under ca
Page 113 and 114:
4.3.2 Phenol-Alcohol Exchange React
Page 115 and 116:
4.4 Reactions with Alkanolamines Ho
Page 117 and 118:
Homometallic Alkoxides 115 R D Pr i
Page 119 and 120:
Homometallic Alkoxides 117 La(OPr i
Page 121 and 122:
Homometallic Alkoxides 119 with the
Page 123 and 124:
Homometallic Alkoxides 121 about 1.
Page 125 and 126:
Homometallic Alkoxides 123 concentr
Page 127 and 128:
Homometallic Alkoxides 125 and othe
Page 129 and 130:
Homometallic Alkoxides 127 Interest
Page 131 and 132:
OH Monofunctional bidentate HC N R
Page 133 and 134:
Homometallic Alkoxides 131 metal al
Page 135 and 136:
Homometallic Alkoxides 133 which yi
Page 137 and 138:
shown in Eq. (2.286): O Mo2(OEt)6 H
Page 139 and 140:
Homometallic Alkoxides 137 Phenyl i
Page 141 and 142:
Homometallic Alkoxides 139 The 1990
Page 143 and 144:
Eqs (2.312)-(2.315): where R D l-ad
Page 145 and 146:
Homometallic Alkoxides 143 On the b
Page 147 and 148:
Homometallic Alkoxides 145 The form
Page 149 and 150:
Homometallic Alkoxides 147 On furth
Page 151 and 152:
4.16 Interactions Between Two Diffe
Page 153 and 154:
4Mo2(OPr i )6 + 18CO (excess) Homom
Page 155 and 156:
isolobality of CR 0 and W⊲OR⊳3
Page 157 and 158:
W2(OR)8 (R = CH2Bu t ) + CO + H2C C
Page 159 and 160:
Homometallic Alkoxides 157 43. J.S.
Page 161 and 162:
Homometallic Alkoxides 159 122. P.N
Page 163 and 164:
Homometallic Alkoxides 161 201. A.
Page 165 and 166:
Homometallic Alkoxides 163 281. R.C
Page 167 and 168:
Homometallic Alkoxides 165 358. L.A
Page 169 and 170:
Homometallic Alkoxides 167 430. M.R
Page 171 and 172:
Homometallic Alkoxides 169 521. I.
Page 173 and 174:
Homometallic Alkoxides 171 N.I. Koz
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Homometallic Alkoxides 177 876. J.
Page 181 and 182:
Homometallic Alkoxides 179 966. H.
Page 183 and 184:
Homometallic Alkoxides 181 1054. M.
Page 185 and 186: 184 Alkoxo and Aryloxo Derivatives
Page 235: 234 Alkoxo and Aryloxo Derivatives
Page 245 and 246: 244 Table 4.3 Alkoxides of aluminiu
Page 249 and 250: 248 Table 4.4 Alkoxides of germaniu
Page 257 and 258: 256 Table 4.6 Alkoxides of scandium
Page 265 and 266: 264 Table 4.7 Alkoxides of lanthani
Page 271 and 272: 270 Table 4.8 (Continued) M-O Bond
Page 277 and 278: 276 Table 4.9 Alkoxides of titanium
Page 279 and 280: 278 Table 4.9 (Continued) Bond leng
Page 287 and 288:
286 Alkoxo and Aryloxo Derivatives
Page 289 and 290:
Page 291 and 292:
Page 293 and 294:
Page 295 and 296:
Page 297 and 298:
Page 299 and 300:
Page 301 and 302:
300 Table 4.11 Alkoxides of chromiu
Page 303 and 304:
302 Table 4.11 (Continued) Metal M-
Page 305 and 306:
304 Table 4.11 (Continued) M-O Bond
Page 307 and 308:
Page 309 and 310:
Page 311 and 312:
Page 313 and 314:
Page 315 and 316:
Page 317 and 318:
316 Table 4.11 (Continued) Metal M-
Page 319 and 320:
Page 321 and 322:
Page 323 and 324:
322 Table 4.12 Alkoxides of mangane
Page 325 and 326:
Page 327 and 328:
Page 329 and 330:
Page 331 and 332:
Page 333 and 334:
332 Table 4.16 Alkoxides of zinc, c
Page 335 and 336:
Page 337 and 338:
Page 339 and 340:
Page 341 and 342:
340 Table 4.17 (Continued) Coordina
Page 343 and 344:
Page 345 and 346:
Page 347 and 348:
Page 349 and 350:
348 Table 4.18 Bimetallic alkoxides
Page 351 and 352:
Page 353 and 354:
Page 355 and 356:
354 Table 4.19 Heterometallic alkox
Page 357 and 358:
Page 359 and 360:
Page 361 and 362:
Page 363 and 364:
Page 365 and 366:
Page 367 and 368:
Page 369 and 370:
Page 371 and 372:
Page 373 and 374:
Page 375 and 376:
Page 377 and 378:
Page 379 and 380:
Page 381 and 382:
Page 383 and 384:
Page 385 and 386:
Page 387 and 388:
Page 389 and 390:
Page 391 and 392:
Page 393 and 394:
Page 395 and 396:
394 Table 5.2 Chemical shifts from
Page 397 and 398:
Page 399 and 400:
Page 401 and 402:
400 Table 5.3 Scandium, yttrium, la
Page 403 and 404:
402 Table 5.3 (continued) Metal Oxo
Page 405 and 406:
Page 407 and 408:
406 Table 5.4 Titanium and zirconiu
Page 409 and 410:
Page 411 and 412:
Page 413 and 414:
Page 415 and 416:
Page 417 and 418:
Page 419 and 420:
Page 421 and 422:
420 Table 5.6 Chromium sub-group me
Page 423 and 424:
Page 425 and 426:
Page 427 and 428:
Page 429 and 430:
Page 431 and 432:
Page 433 and 434:
Page 435 and 436:
Page 437 and 438:
Page 439 and 440:
Page 441 and 442:
Page 443 and 444:
Page 445 and 446:
1 INTRODUCTION 6 Metal Aryloxides T
Page 447 and 448:
Metal Aryloxides 447 or both of the
Page 449 and 450:
R1 OH O R2 R3NH2 −H2O Scheme 6.3
Page 451 and 452:
Cl S N N OH O Cl Me 3C NH HN OH HO
Page 453 and 454:
N OH N OH Me 3C Me3C HO HO N N OH H
Page 455 and 456:
Metal Aryloxides 455 2Ln C 3Hg⊲C6
Page 457 and 458:
Metal Aryloxides 457 Mixed halo, ar
Page 459 and 460:
product metal aryloxide 1e,1f (Eqs
Page 461 and 462:
Metal Aryloxides 461 Eqs 6.39 and 6
Page 463 and 464:
O Mg Mg OAr O Metal Aryloxides 463
Page 465 and 466:
3.7 From Metal Hydrides Metal Arylo
Page 467 and 468:
Metal Aryloxides 467 Two other impo
Page 469 and 470:
Metal Aryloxides 469 Table 6.1 Meta
Page 471 and 472:
Table 6.3 W-OAr distances for vario
Page 473 and 474:
Metal Aryloxides 473 At first it is
Page 475 and 476:
Zr−O distance (Å) V−O distance
Page 477 and 478:
Metal Aryloxides 477 as expected ar
Page 479 and 480:
Metal Aryloxides 479 whereas R D Me
Page 481 and 482:
where OAr = O But But H3C H3C O Ta
Page 483 and 484:
PPh 2 Ph P Pt OAr PPh2 where OAr =
Page 485 and 486:
6 SURVEY OF METAL ARYLOXIDES 6.1 Sp
Page 487 and 488:
487 Na2[V(O) 2(OAr) 2]2.4H2O.DMF 6-
Page 489 and 490:
489 [Tc(O)(OAr)(di-OAr)] 8-quin 2.0
Page 491 and 492:
491 [Ni3⊲OAr⊳6][ClO4].EtOH 8-qu
Page 493 and 494:
493 [Pt(OAr⊳2](tcnq) sq. planar P
Page 495 and 496:
495 [Al(OAr) 3].MeOH 8-quin 1.850 (
Page 497 and 498:
497 [Sb(OAr) 2⊲S2COEt⊳] pentago
Page 499 and 500:
499 [Tc(O)(OAr)(N-salicylideneDD-gl
Page 501 and 502:
Metal Aryloxides 501 A contribution
Page 503 and 504:
503 Table 6.8 Metal bi-phenolates B
Page 505 and 506:
505 Table 6.9 Metal binaphtholates
Page 507 and 508:
507 [TiCl2(di-OAr)]2 two tetrahedra
Page 509 and 510:
Metal Aryloxides 509 co-workers hav
Page 511 and 512:
511 [Li⊲ 2-OAr⊳]3 planar Li3O3
Page 513 and 514:
513 Table 6.11 Sodium aryloxides Bo
Page 515 and 516:
Table 6.12 Potassium aryloxides Met
Page 517 and 518:
Table 6.15 Magnesium aryloxides Met
Page 519 and 520:
519 Table 6.18 Barium aryloxides Bo
Page 521 and 522:
521 Table 6.19 Group 3 metal and la
Page 523 and 524:
523 [Me4N]La2Na2⊲ 4-OAr⊳⊲ 3-O
Page 525 and 526:
525 [Nd⊲OC6H3Ph- 6-C6H5⊳⊲OC6H
Page 527 and 528:
527 [⊲THF⊳Li⊲ 2-OAr⊳2Sm⊲C
Page 529 and 530:
529 [Eu⊲ 2-OAr⊳4⊲OAr⊳2⊲ 3
Page 531 and 532:
531 [Yb(OAr) 3⊲THF⊳2].THF squar
Page 533 and 534:
Metal Aryloxides 533 carbon atoms a
Page 535 and 536:
535 [Cp Ł Th(OAr)⊲CH2SiMe3⊳2]
Page 537 and 538:
Metal Aryloxides 537 amido compound
Page 539 and 540:
539 Table 6.21 Titanium aryloxides
Page 541 and 542:
541 [Ti2⊲ 2-OAr⊳2(OAr) 2Cl4]2 e
Page 543 and 544:
543 [Ti(OAr) 2⊲NMe2⊳2] tetrahed
Page 545 and 546:
545 [Ti(OAr) 3Bu t ] tetrahedral Ti
Page 547 and 548:
547 [⊲ArO⊳2Ti⊲ 2-ButNDCC4Et4C
Page 549 and 550:
549 [Cp⊲C5H3Me-Pri-1,2)Ti(OAr)Cl]
Page 551 and 552:
551 [CpTi(OAr) 2⊲HPPh⊳] OC6H3Pr
Page 553 and 554:
553 [Ti⊲di-OAr⊳Cl2].THF 6-coord
Page 555 and 556:
555 Table 6.22 Zirconium aryloxides
Page 557 and 558:
557 [Zr(Ind-OAr) 2] 1-indenylphenox
Page 559 and 560:
559 [Cp2Zr(OAr)] 18-electron Zr, tw
Page 561 and 562:
Metal Aryloxides 561 The thermal st
Page 563 and 564:
Metal Aryloxides 563 can only arise
Page 565 and 566:
565 1.839 (2) 138 1.854 (2) 140 [(t
Page 567 and 568:
567 [V(OAr) 3-N-Li(THF) 3] tetrahed
Page 569 and 570:
569 [V(O)(di-OAr)] 6-coord. V, both
Page 571 and 572:
571 cis,mer-[Nb(OAr) 2Cl3(THF)] dis
Page 573 and 574:
573 [Nb⊲OC6H3Ph- 4-C6H7⊳⊲OAr
Page 575 and 576:
575 Table 6.26 Tantalum aryloxides
Page 577 and 578:
577 [(THF)(ArO) 3Ta⊲DNND⊳Ta(OAr
Page 579 and 580:
579 [Ta(OAr) 2Cl2⊲CH2C6H5⊳] tbp
Page 581 and 582:
581 [Ta(OAr) 2Cl⊲ 6-C6Me6⊳] OC6
Page 583 and 584:
583 [Ta(OAr)⊲OC6H3Pri- 2-CMeDCH2
Page 585 and 586:
585 [f(TMEDA)Na⊲ 2-OAr⊳2g2Cr] 4
Page 587 and 588:
587 Table 6.28 Molybdenum aryloxide
Page 589 and 590:
589 [Mo2⊲OAr⊳5⊲NMe2⊳⊲HNMe
Page 591 and 592:
591 [Mo(Hdi-OAr) 2] 6-coord. Mo, on
Page 593 and 594:
593 [W2⊲OAr⊳6⊲HNMe2⊳2] OC6F
Page 595 and 596:
595 [W(OAr) 2⊲DNBu t ⊳2] OC6H3P
Page 597 and 598:
597 [W(OC6H3Ph- 1-C6H4⊳2⊲PMePh2
Page 599 and 600:
599 [W⊲OC6HPh3- 1-C6H4-c-C5H8C- O
Page 601 and 602:
601 [⊲OC⊳3Mn⊲C4H4N⊳Mn⊲CO3
Page 603 and 604:
603 Table 6.32 Simple aryloxides of
Page 605 and 606:
Page 607 and 608:
607 [NEt4]3fFe6⊲ 4-S⊳4⊲OAr⊳
Page 609 and 610:
609 [Ru(OAr) 2(CO)(py-CMeO-4)] cis-
Page 611 and 612:
Table 6.35 Simple aryloxides of osm
Page 613 and 614:
Metal Aryloxides 613 states, e.g. [
Page 615 and 616:
Bu t O Bu t (6-I) Bu t Bu t O Metal
Page 617 and 618:
6.2.10 Group 9 Metal Aryloxides Met
Page 619 and 620:
Table 6.38 Simple aryloxides of iri
Page 621 and 622:
Metal Aryloxides 621 Table 6.39 (Co
Page 623 and 624:
623 [Pd(OAr)⊲C6H3fCH2NMe2g2-2,6)]
Page 625 and 626:
Metal Aryloxides 625 Table 6.41 Sim
Page 627 and 628:
Page 629 and 630:
629 [(RNC) 2Cu⊲ 2-OAr⊳2Cu(CNR)
Page 631 and 632:
Metal Aryloxides 631 The two-coordi
Page 633 and 634:
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
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:
Page 673 and 674:
Page 675 and 676:
Page 677 and 678:
Page 679 and 680:
Page 681 and 682:
Page 683 and 684:
Page 685 and 686:
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 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
show all

2 Homometallic Alkoxides

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?