Research inspired by the chemistry of nitrogenase - Novel metal complexes and their reactivity toward dinitrogen, nitriles, and alkynes

被引:92
作者
Hidai, M [1 ]
Mizobe, Y
机构
[1] Tokyo Univ Sci, Fac Ind Sci & Technol, Dept Mat Sci & Technol, Chiba 2788510, Japan
[2] Univ Tokyo, Inst Ind Sci, Meguro Ku, Tokyo 1538505, Japan
关键词
nitrogen fixation; molybdenum and tungsten dinitrogen complexes; ruthenium thiolato complexes; metal sulfido clusters; nitriles; alkynes;
D O I
10.1139/V05-016
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Summarized here are our continuous studies of the last three decades concerning syntheses of new types of complexes learned from nitrogenase and their reactivites toward dinitrogen, nitriles, and alkynes. For Mo and W dinitrogen complexes with tertiary phosphine coligands, a variety of their intriguing reactivities have been demonstrated, and novel transformations of the N-2 ligands into numerous nitrogen-containing ligands and compounds have been developed. The CN bond cleavage of certain nitriles also proceeds on the Mo site surrounded by tertiary phosphines. Stimulated by the sophisticated structure of the active site of nitrogenase, multinuclear metal-sulfur complexes have been synthesized in rational ways. New types of stoichiometric and catalytic reactions of alkynes have been found by using the thiolato-bridged diruthenium complexes and some cubane-type sulfido clusters containing a noble metal.
引用
收藏
页码:358 / 374
页数:17
相关论文
共 176 条
[31]   The mechanism of nitrogenase. Computed details of the site and geometry of binding of alkyne and alkene substrates and intermediates [J].
Dance, I .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (38) :11852-11863
[32]   Understanding structure and reactivity of new fundamental inorganic molecules: metal sulfides, metallocarbohedrenes, and nitrogenase [J].
Dance, I .
CHEMICAL COMMUNICATIONS, 1998, (05) :523-530
[33]   Catalytic reduction of hydrazine to ammonia with MoFe3S4-polycarboxylate clusters. Possible relevance regarding the function of the molybdenum-coordinated homocitrate in nitrogenase [J].
Demadis, KD ;
Malinak, SM ;
Coucouvanis, D .
INORGANIC CHEMISTRY, 1996, 35 (13) :4038-4046
[34]   PREPARATION AND REACTIONS OF DIRUTHENIUM THIOLATE COMPLEXES [CPSTARRU(MU-SR)3RUCPSTAR] (CPSTAR=ETA-5-C5ME5 R = I-PR, ET, CY, BZ, PH) [J].
DEV, S ;
MIZOBE, Y ;
HIDAI, M .
INORGANIC CHEMISTRY, 1990, 29 (23) :4797-4801
[35]   PREPARATION, PROPERTIES, AND SOME REACTIONS OF NOVEL RUTHENIUM THIOLATE COMPLEXES [J].
DEV, S ;
IMAGAWA, K ;
MIZOBE, Y ;
CHENG, GB ;
WAKATSUKI, Y ;
YAMAZAKI, H ;
HIDAI, M .
ORGANOMETALLICS, 1989, 8 (05) :1232-1237
[36]   THE CHEMISTRY OF NIOBIUM AND TANTALUM DITHIOCARBAMATO-COMPLEXES .1. SYNTHESIS, STRUCTURE, AND PROTONATION OF DINITROGEN-BRIDGED COMPLEXES [J].
DILWORTH, JR ;
HENDERSON, RA ;
HILLS, A ;
HUGHES, DL ;
MACDONALD, C ;
STEPHENS, AN ;
WALTON, DRM .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1990, (03) :1077-1085
[37]   CATALYTIC APPLICATIONS OF TRANSITION-METAL COMPLEXES WITH SULFIDE LIGANDS [J].
DUBOIS, MR .
CHEMICAL REVIEWS, 1989, 89 (01) :1-9
[38]   Nitrogenase MoFe-protein at 1.16 Å resolution:: A central ligand in the FeMo-cofactor [J].
Einsle, O ;
Tezcan, FA ;
Andrade, SLA ;
Schmid, B ;
Yoshida, M ;
Howard, JB ;
Rees, DC .
SCIENCE, 2002, 297 (5587) :1696-1700
[39]   MOLECULAR ENGINEERING OF SOLID-STATE MATERIALS - ORGANOMETALLIC BUILDING-BLOCKS [J].
FAGAN, PJ ;
WARD, MD ;
CALABRESE, JC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (05) :1698-1719
[40]   WITTIG-LIKE REACTIONS OF TUNGSTEN ALKYLIDYNE COMPLEXES [J].
FREUDENBERGER, JH ;
SCHROCK, RR .
ORGANOMETALLICS, 1986, 5 (02) :398-400