Thiophene and butadiene-thiolate complexes of molybdenum: Observations relevant to the mechanism of hydrodesulfurization

被引：45

作者：

Janak, KE ^{[1
]}

Tanski, JM ^{[1
]}

Churchill, DG ^{[1
]}

Parkin, G ^{[1
]}

机构：

[1] Columbia Univ, Dept Chem, New York, NY 10027 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 16期

关键词：

D O I：

10.1021/ja012771o

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Mo(PMe3)6 reacts with thiophene to give the η5-thiophene complex (η5-C4H4S)Mo(PMe3)3 and the η5-butadiene-thiolate complex (η5-C4H5S)Mo(PMe3)2(η2-CH2PMe2), which are the first examples of (i) η5-thiophene coordination and (ii) C-S cleavage and hydrogenation by a molybdenum compound. Deuterium labeling studies suggest that the hydrogenation of thiophene may involve an alkylidene intermediate, an observation that has ramifications for the mechanisms of hydrodesulfurization. Copyright © 2002 American Chemical Society.

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页码：4182 / 4183

页数：2

相关论文

共 17 条

[1] Thiophenes in organotransition metal chemistry: Patterns of reactivity [J].

Angelici, RJ .

ORGANOMETALLICS, 2001, 20 (07) :1259-1275

[2] STRUCTURAL ASPECTS OF THIOPHENE COORDINATION IN TRANSITION-METAL COMPLEXES [J].

ANGELICI, RJ .

COORDINATION CHEMISTRY REVIEWS, 1990, 105 :61-76

[3] OPENING, DESULFURIZATION, AND HYDROGENATION OF THIOPHENE AT IRIDIUM - AN EXPERIMENTAL-STUDY IN A HOMOGENEOUS PHASE [J].

BIANCHINI, C ;

MELI, A ;

PERUZZINI, M ;

VIZZA, F ;

FREDIANI, P ;

HERRERA, V ;

SANCHEZDELGADO, RA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (07) :2731-2742

[4] Modeling aspects of hydrodesulfurization at molybdenum:: Carbon-sulfur bond cleavage of thiophenes by Ansa molybdenocene complexes [J].

Churchill, DG ;

Bridgewater, BM ;

Parkin, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (01) :178-179

[5] Pentadienyl ligands: Their properties, potential, and contributions to inorganic and organometallic chemistry [J].

Ernst, RD .

COMMENTS ON INORGANIC CHEMISTRY, 1999, 21 (4-6) :285-325

[6] C-S BOND-CLEAVAGE IN A PI-THIOPHENE RUTHENIUM COMPLEX [J].

HACHGENEI, JW ;

ANGELICI, RJ .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1987, 26 (09) :909-910

[7] CARBON SULFUR BOND-CLEAVAGE IN CPRU(ETA-5-THIOPHENE)+ AND SUBSEQUENT REACTIONS OF THE BUTADIENE-THIOLATE PRODUCT [J].

HACHGENEI, JW ;

ANGELICI, RJ .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1988, 355 (1-3) :359-378

[8] CARBON SULFUR BOND-CLEAVAGE IN THIOPHENE BY GROUP-6 METALLOCENES [J].

JONES, WD ;

CHIN, RM ;

CRANE, TW ;

BARUCH, DM .

ORGANOMETALLICS, 1994, 13 (11) :4448-4452

[9] Atomic-scale structure of Co-Mo-S nanoclusters in hydrotreating catalysts [J].

Lauritsen, JV ;

Helveg, S ;

Lægsgaard, E ;

Stensgaard, I ;

Clausen, BS ;

Topsoe, H ;

Besenbacher, E .

JOURNAL OF CATALYSIS, 2001, 197 (01) :1-5

[10] A NEW MECHANISM FOR METAL-CATALYZED THIOPHENE HYDROGENOLYSIS - PROTON-INDUCED C-S CLEAVAGE OF COORDINATED THIOPHENE IN SOLUTION AND IN THE SOLID-STATE [J].

LUO, SF ;

RAUCHFUSS, TB ;

GAN, ZH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (11) :4943-4944