Stepwise oxidation of benzylamine coordinated to the [Tp'W(CO)(PhC(2)Me)](+) moiety

被引：51

作者：

Gunnoe, TB ^{[1
]}

White, PS ^{[1
]}

Templeton, JL ^{[1
]}

机构：

[1] UNIV N CAROLINA,DEPT CHEM,CHAPEL HILL,NC 27599

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1996年 / 118卷 / 29期

关键词：

D O I：

10.1021/ja953944a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Coordination of benzylamine to the [Tp'W(CO)(PhC(2)Me)](+) moiety activates the amine for stepwise oxidation by sequential hydride/proton removal steps. Each metal complex along the stepwise reaction path (amine, amido, imine, azavinylidene, and nitrile) has been isolated and characterized. The structure of the imine complex [Tp'W(CO)(PhC(2)Me)(NH double bond CHPh)][BF4] (4) has been confirmed by an X-ray diffraction study. Complex 4 crystallizes in the space group P2(1)/c (Z = 4, a = 13.790(3) Angstrom, b = 13.225(3) Angstrom, c = 19.150(4) Angstrom, beta = 108.769(1)degrees, R = 3.5%, R(w) = 4.4%), and key geometric features include a W-N dative bond length of 2.135(6) Angstrom to the imine nitrogen and a W-N-C angle of 129.7(5).

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页码：6916 / 6923

页数：8

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共 54 条

[1] OXIDATION OF ISOPROPYLAMINE COORDINATED TO RUTHENIUM [J].

ADCOCK, PA ;

KEENE, FR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (21) :6494-6495

[2] CH3CN INSERTION REACTIONS OF (C5H4R)2ZR(R)(L)+ COMPLEXES [J].

ALELYUNAS, YW ;

JORDAN, RF ;

ECHOLS, SF ;

BORKOWSKY, SL ;

BRADLEY, PK .

ORGANOMETALLICS, 1991, 10 (05) :1406-1416

[3] SYNTHESIS AND PROPERTIES OF SOME TETRAAMMINERUTHENIUM(II) COMPLEXES OF BIDENTATE LIGANDS, CIS-RU(NH3)4(X-Y)2+ [J].

ALVAREZ, VE ;

ALLEN, RJ ;

MATSUBAR.T ;

FORD, PC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (25) :7686-7692

[4] REACTIONS OF ALKYL AND HYDRIDE DERIVATIVES OF PERMETHYLSCANDOCENE AND PERMETHYLZIRCONOCENE WITH NITRILES AND AMINES - CATALYTIC-HYDROGENATION OF TERT-BUTYL CYANIDE WITH PERMETHYLSCANDOCENE HYDRIDE [J].

BERCAW, JE ;

DAVIES, DL ;

WOLCZANSKI, PT .

ORGANOMETALLICS, 1986, 5 (03) :443-450

[5] INSERTION REACTIONS OF NITRILES IN CATIONIC ALKYLBIS(CYCLOPENTADIENYL)TITANIUM COMPLEXES - THE FACILE SYNTHESIS OF AZAALKENYLIDENE TITANIUM COMPLEXES AND THE CRYSTAL AND MOLECULAR-STRUCTURE OF [(INDENYL)2TI(NCMEPH)(NCPH)]BPH4 [J].

BOCHMANN, M ;

WILSON, LM ;

HURSTHOUSE, MB ;

MOTEVALLI, M .

ORGANOMETALLICS, 1988, 7 (05) :1148-1154

[6] SYNTHESIS AND CHEMISTRY OF CP2ZR(PH)(THF)+ - SELECTIVITY OF PROTOLYTIC AND OXIDATIVE ZR-R BOND-CLEAVAGE REACTIONS [J].

BORKOWSKY, SL ;

JORDAN, RF ;

HINCH, GD .

ORGANOMETALLICS, 1991, 10 (05) :1268-1274

[7] [(3,5-(CF3)2C6H3)4B]-[H(OET2)2]+ - A CONVENIENT REAGENT FOR GENERATION AND STABILIZATION OF CATIONIC, HIGHLY ELECTROPHILIC ORGANOMETALLIC COMPLEXES [J].

BROOKHART, M ;

GRANT, B ;

VOLPE, AF .

ORGANOMETALLICS, 1992, 11 (11) :3920-3922

[8] OXIDATION OF COORDINATED DIAMINES IN BIS(2,2'-BIPYRIDINE) COMPLEXES OF RUTHENIUM [J].

BROWN, GM ;

WEAVER, TR ;

KEENE, FR ;

MEYER, TJ .

INORGANIC CHEMISTRY, 1976, 15 (01) :190-196

[9] ZIRCONOCENE COMPLEXES OF IMINES - GENERAL-SYNTHESIS, STRUCTURE, REACTIVITY, AND INSITU GENERATION TO PREPARE GEOMETRICALLY PURE ALLYLIC AMINES [J].

BUCHWALD, SL ;

WATSON, BT ;

WANNAMAKER, MW ;

DEWAN, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (12) :4486-4494

[10] OPTICAL RESOLUTION AND REACTIVITY OF CHIRAL TUNGSTEN ALKYNE COMPLEXES [J].

CALDARELLI, JL ;

WHITE, PS ;

TEMPLETON, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (26) :10097-10103

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