C-H and C-S bond cleavage in uranium(III) thiolato complexes

被引：46

作者：

Arliguie, T ^{[1
]}

Lescop, C ^{[1
]}

Ventelon, L ^{[1
]}

Leverd, PC ^{[1
]}

Thuéry, P ^{[1
]}

Nierlich, M ^{[1
]}

Ephritikhine, M ^{[1
]}

机构：

[1] CEA Saclay, CNRS URA 331, DSM,DRECAM, Serv Chim Mol, F-91191 Gif Sur Yvette, France

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 17期

关键词：

D O I：

10.1021/om0102551

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reduction of the uranium(IV) thiolates Cp*U-2(SR)(2) (Cp* = eta -C5Me5, R = Ph, Me, Pr-i or Bu-t) with sodium amalgam afforded the corresponding U(III) complexes Na[Cp*U-2(SR)(2)] (R = Ph, 2a; Me, 2b; Pr-i, 2c) or the U(IV) sulfide Na[Cp*U-2((SBu)-Bu-t)(S)]. C-S bond cleavage of a thiolate ligand was also observed during the thermal decomposition of 2c into the sulfide Na[Cp*U-2((SPr)-Pr-i)(S)], whereas 2b was transformed in refluxing THF into the thiametallacyclopropane complex Na[Cp*U-2(SMe)(SCH2)], resulting from C-H bond activation of a SMe group. The X-ray crystal structures of [Na(18-crown-6)(THF)(2)][Cp*U-2((SPr)-Pr-i)(2)], [Na(18-crown-6)] [Cp*U-2((SBu)-Bu-t)(S)], and [Na(18-crown-6)(THF)(2)][Cp*U-2(SMe)(SCH2)] have been determined.

引用

页码：3698 / 3703

页数：6

共 59 条

[1] ASPECTS OF THE HYDROGENATION OF CARBON-DISULFIDE BY TRANSITION-METAL CLUSTER COMPOUNDS - THE REACTIONS OF CARBON-DISULFIDE WITH HYDRIDOTRIOSMIUM-CARBONYL CLUSTERS [J].

ADAMS, RD ;

GOLEMBESKI, NM ;

SELEGUE, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (03) :546-555

[2] TRANSFORMATIONS OF A METHYLENE LIGAND IN A METAL CLUSTER CONTAINING SULFUR - A MODEL FOR SULFUR POISONING IN A MOLECULAR-COMPLEX [J].

ADAMS, RD ;

BABIN, JE ;

TASI, M .

ORGANOMETALLICS, 1987, 6 (08) :1717-1727

[3]

[Anonymous], 1999, SHELXTL VERSION 5 1

[4] ANIONIC TRISCYCLOPENTADIENYLURANIUM(III) HYDRIDES [J].

BERTHET, JC ;

VILLIERS, C ;

LEMARECHAL, JF ;

DELAVAUX-NICOT, B ;

LANCE, M ;

NIERLICH, M ;

VIGNER, J ;

EPHRITIKHINE, M .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 440 (1-2) :53-65

[5] Hydrogenation, hydrogenolysis, and desulfurization of thiophenes by soluble metal complexes: Recent achievements and future directions [J].

Bianchini, C ;

Meli, A .

ACCOUNTS OF CHEMICAL RESEARCH, 1998, 31 (03) :109-116

[6] THIOLATO-COMPLEXES OF THE TRANSITION-METALS [J].

BLOWER, PJ ;

DILWORTH, JR .

COORDINATION CHEMISTRY REVIEWS, 1987, 76 :121-185

[7] THERMAL DEPOSITION OF TIS FILMS FROM VOLATILE TI(SBUT)4 [J].

BOCHMANN, M ;

HAWKINS, I ;

WILSON, LM .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (05) :344-345

[8] HETEROBIMETALLIC COMPLEXES BRIDGED BY A SINGLE 4E SULFUR LIGAND - ADDITION OF M'(CO)(5) (M'=CR, MO, W) TO THE TA=S BOND OF (T-BUC(5)H(4))(2)TA(S)H [J].

BRUNNER, H ;

CHALLET, S ;

KUBICKI, MM ;

LEBLANC, JC ;

MOISE, C ;

VOLPATO, F ;

WACHTER, J .

ORGANOMETALLICS, 1995, 14 (08) :3623-3624

[9] SYNTHESIS, STRUCTURE, AND REACTIVITY OF TRIMETHYLPHOSPHINE ZIRCONOCENE THIOALDEHYDE COMPLEXES [J].

BUCHWALD, SL ;

NIELSEN, RB ;

DEWAN, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (05) :1590-1591

[10] KINETICS AND SUBSTITUENT EFFECTS IN THE FORMATION OF ZIRCONOCENE THIOALDEHYDE COMPLEXES - BETA-HYDRIDE ELIMINATION VERSUS CYCLOMETALATION [J].

BUCHWALD, SL ;

NIELSEN, RB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (10) :3171-3175

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