Facile conversion of an appended silylamido to a silyloxy ligand via isocyanate elimination. Synthesis of {[(C(5)Me(4))SiMe(2)O]Zr(eta(2)-O(2)CMe)(mu-O(2)CMe)}(2) via the carboxylation of [(C(5)Me(4))SiMe(2)(N-t-Bu)]ZrMe(2)

被引：44

作者：

Kloppenburg, L ^{[1
]}

Petersen, JL ^{[1
]}

机构：

[1] W VIRGINIA UNIV,DEPT CHEM,MORGANTOWN,WV 26506

来源：

ORGANOMETALLICS | 1996年 / 15卷 / 01期

关键词：

D O I：

10.1021/om9508086

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of 2 equiv of CO2 with [(C(5)Me(4))SiMe(2)(N-t-Bu)]ZrMe(2) proceeds with the formation of {[(C(5)Me(4))SiMe(2)(N-t-Bu)]Zr(eta(2)-O(2)CMe)(mu-O(2)CMe)}(2) (2), which reacts with additional CO2 to afford {[(C(5)Me(4))SiMe(2)O]Zr(eta 2-O(2)CMe)(mu-O(2)CMe)}(2) (3) with the concomitant elimination of OCN-t-Bu. The formation of OCN-t-Bu was confirmed by a combination of GC/MS and IR measurements; the molecular structures of 2 and 3 were determined by X-ray crystallography.

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页码：7 / 9

页数：3

相关论文

共 18 条

[1] SYNTHESIS OF ETA-CYCLOPENTADIENYLIDENE-4-IMIDOPROPYLNIOBIUM DERIVATIVES [NB(ETA-SIGMA-C5H4(CH2)3N)CL2] AND [NB(ETA-SIGMA-C5H4(CH2)3N)(PME3)CL2] [J].

ANTONELLI, DM ;

GREEN, MLH ;

MOUNTFORD, P .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 438 (1-2) :C4-C8

[2]

Canich J. A., 1991, European Patent Application, Patent No. [EP 0 420 436 A1, 0420436]

[3]

CANICH JM, 1836, Patent No. 542236

[4] SYNTHESIS, CHARACTERIZATION, AND EQUILIBRIUM STUDIES OF GROUP 6B INTRAMOLECULAR METALLOESTERS - CRYSTAL-STRUCTURE OF TRANS-(ETA-5-C5H4)CH2CH2O2CW(CO)2PPH3 [J].

COOLBAUGH, TS ;

SANTARSIERO, BD ;

GRUBBS, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (21) :6310-6318

[5] CHLOROZIRCONOCENE CARBOXYLATE COMPLEXES CP2CLZR(OCOH), CP2CLZR(OCOCH3), CP2CLZR(OCO-TERT-BU), CP2CLZR(OCOPH) AND THEIR REACTIONS WITH ZIRCONIUM HYDRIDE REAGENTS - METAL HYDRIDE REDUCTION OF LIGATED CARBOXYLATE [J].

CUTLER, A ;

RAJA, M ;

TODARO, A .

INORGANIC CHEMISTRY, 1987, 26 (17) :2877-2881

[6]

DUPLOOY KE, 1995, J ORGANOMETALLICS, V14, P3129

[7] INTRAMOLECULAR C-X ACTIVATION AS A SYNTHETIC ROUTE TO BIDENTATE CYCLOPENTADIENYL-ALKOXIDE LIGANDS - PREPARATION AND MOLECULAR-STRUCTURE OF (3-(2,3,4,5-TETRAMETHYLCYCLOPENTADIENYL)PROPOXY)TITANIUM DICHLORIDE [J].

FANDOS, R ;

MEETSMA, A ;

TEUBEN, JH .

ORGANOMETALLICS, 1991, 10 (01) :59-60

[8] STRUCTURAL AND CHEMICAL ASPECTS OF ELECTRON DEFICIENT PENTAMETHYLCYCLOPENTADIENYLTITANIUM HALIDES, ALKYLS, AND OXIDES [J].

GOMEZSAL, MP ;

MENA, M ;

ROYO, P ;

SERRANO, R .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1988, 358 (1-3) :147-159

[9] SYNTHESIS AND CHARACTERIZATION OF BRIDGED HALF-SANDWICH AMIDES OF TITANIUM AND ZIRCONIUM [J].

HERRMANN, WA ;

MORAWIETZ, MJA .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1994, 482 (1-2) :169-181

[10] EFFICIENT NEW SYNTHETIC ROUTE TO BIDENTATE, MONOMERIC CYCLOPENTADIENYL AMIDE COMPLEXES OF GROUP-4 TRANSITION-METALS - SYNTHESIS AND CHARACTERIZATION OF THE ZIRCONIUM AND HAFNIUM COMPLEXES [(ETA(5)-SIGMA-C5H4(CH2)3NME)MX2(NHME2)] (X = CL, I, M = ZR - X = I, M = HF) AND [(ETA(5)-SIGMA-C5H4(CH2)3NME)ZRX2] (X = NME2, CH2PH, CH2SIME3, BH4) AND MOLECULAR-STRUCTURE OF [(ETA(5)-SIGMA-C5H4(CH2)3NME)ZRCL(CH2PH)]2 [J].

HUGHES, AK ;

MEETSMA, A ;

TEUBEN, JH .

ORGANOMETALLICS, 1993, 12 (05) :1936-1945