DIHYDROGEN COMPLEXES IN CATALYSIS - ISOTOPE EXCHANGE-REACTIONS

被引:71
作者
ALBENIZ, AC [1 ]
HEINEKEY, DM [1 ]
CRABTREE, RH [1 ]
机构
[1] YALE UNIV,STERLING CHEM LAB,NEW HAVEN,CT 06511
关键词
D O I
10.1021/ic00019a012
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Dihydrogen complexes [CpRu(CO)(PR3)(eta-2-H-2)]X (R = Ph (1), Cy (2); X = BF4-, CF3SO3-), [Ru(dppe)H-2(eta-2-H-2)]BF4 (3), and [Ir(bq)(PPh3)H-2(eta-2-H-2)]SbF6 (5) were tested as catalysts for H/D exchange between ROH and D2. Complex 5 is the most efficient, while 3 is moderately active and 1 and 2 are essentially inactive. Maximum activity arises when an M-H group is cis to a coordination site capable of binding both H-2 and ROH. The relevance of these results to the mechanism of H/D exchange in hydrogenase is also discussed.
引用
收藏
页码:3632 / 3635
页数:4
相关论文
共 35 条
[1]  
[Anonymous], BIOORGANIC CHEM NICK
[2]  
Arnett E. M., 1970, J AM CHEM SOC, V92, P1260
[3]   QUANTITATIVE COMPARISONS OF WEAK ORGANIC BASES [J].
ARNETT, EM .
PROGRESS IN PHYSICAL ORGANIC CHEMISTRY, 1963, 1 :223-403
[4]   NMR PROPERTIES OF THE COMPLEXES TRANS-[M(ETA-2-H2)(H)(PET2CH2CH2PET2)2]+, M = FE, RU, OS - INTRAMOLECULAR EXCHANGE OF ATOMS BETWEEN ETA-2-DIHYDROGEN AND HYDRIDE LIGANDS [J].
BAUTISTA, M ;
EARL, KA ;
MORRIS, RH ;
SELLA, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (12) :3780-3782
[5]   CLASSICAL AND NONCLASSICAL POLYHYDRIDE RUTHENIUM(II) COMPLEXES STABILIZED BY THE TETRAPHOSPHINE P(CH2CH2PPH2)3 [J].
BIANCHINI, C ;
PEREZ, PJ ;
PERUZZINI, M ;
ZANOBINI, F ;
VACCA, A .
INORGANIC CHEMISTRY, 1991, 30 (02) :279-287
[6]   EVIDENCE FOR A MOLECULAR-HYDROGEN COMPLEX OF RHODIUM - SOME FACTORS AFFECTING CIS-DIHYDRIDE REVERSIBLE ETA-2-DIHYDROGEN EXCHANGE [J].
BIANCHINI, C ;
MEALLI, C ;
PERUZZINI, M ;
ZANOBINI, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (18) :5548-5549
[7]  
CAPELLANI EP, 1989, INORG CHEM, V28, P4437
[8]   HIGHLY REACTIVE DIHYDROGEN COMPLEXES OF RUTHENIUM AND RHENIUM - FACILE HETEROLYSIS OF COORDINATED DIHYDROGEN [J].
CHINN, MS ;
HEINEKEY, DM ;
PAYNE, NG ;
SOFIELD, CD .
ORGANOMETALLICS, 1989, 8 (07) :1824-1826
[9]   SYNTHESIS AND PROPERTIES OF A SERIES OF RUTHENIUM DIHYDROGEN COMPLEXES [J].
CHINN, MS ;
HEINEKEY, DM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (19) :5865-5867
[10]   DIHYDROGEN COMPLEXES OF RUTHENIUM .2. KINETIC AND THERMODYNAMIC CONSIDERATIONS AFFECTING PRODUCT DISTRIBUTION [J].
CHINN, MS ;
HEINEKEY, DM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (13) :5166-5175