Lewis vs. Bronsted-basicities of diiron dithiolates:: spectroscopic detection of the "rotated structure'' and remarkable effects of ethane- vs. propanedithiolate

被引：43

作者：

Justice, Aaron K. ^{[1
]}

Zampella, Giuseppe

De Gioia, Luca

Rauchfuss, Thomas B.

机构：

[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA

[2] Univ Milano Bicocca, Dept Biosci & Biotechnol, I-20126 Milan, Italy

来源：

CHEMICAL COMMUNICATIONS | 2007年 / 20期

关键词：

D O I：

10.1039/b700754j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The new complexes Fe-2(S(2)CnH(2)n)(CO)(2)(dppv)(2) (n = 2, 3; dppv = cis-1,2-C2H2(PPh2)(2)) form adducts with AlBr3 and B(C6F5)(3), which adopt the "rotated structure" proposed for the active site of the Fe-only hydrogenases - the propanedithiolate is significantly more Lewis basic due to nonbonded interactions between the dithiolate strap and the ligands on Fe.

引用

收藏

页码：2019 / 2021

页数：3

相关论文

共 19 条

[1] LEWIS ACID PROMOTED TERMINAL-TO-BRIDGE CARBONYL SHIFT IN [(PI-C5H5)RU(CO)2]2 [J].

ALICH, A ;

NELSON, NJ ;

SHRIVER, DF .

JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS, 1971, (06) :254-&

[2] Tris(pentafluorophenyl)borane: a special boron Lewis acid for special reactions [J].

Erker, G .

DALTON TRANSACTIONS, 2005, (11) :1883-1890

[3] Fundamental properties of small molecule models of Fe-only hydrogenase: computations relative to the definition of an entatic state in the active site [J].

Georgakaki, IP ;

Thomson, LM ;

Lyon, EJ ;

Hall, MB ;

Darensbourg, MY .

COORDINATION CHEMISTRY REVIEWS, 2003, 238 :255-266

[4]

Georgekaki I. P., 2004, COMP COORD CHEM 2, VII, P549

[5] Bimetallic carbonyl thiolates as functional models for Fe-only hydrogenases [J].

Gloaguen, F ;

Lawrence, JD ;

Rauchfuss, TB ;

Bénard, M ;

Rohmer, MM .

INORGANIC CHEMISTRY, 2002, 41 (25) :6573-6582

[6]

HORWITZ CP, 1984, ADV ORGANOMET CHEM, V23, P219

[7]

Jaouen G, 2006, BIOORGANOMETALLICS: BIOMOLECULES, LABELING, MEDICINE, P1

[8] Chelate control of diiron(I) dithiolates relevant to the [Fe-Fe]-hydrogenase active site [J].

Justice, Aaron K. ;

Zampella, Giuseppe ;

De Gioia, Luca ;

Rauchfuss, Thomas B. ;

van der Vlugt, Jarl Ivar ;

Wilson, Scott R. .

INORGANIC CHEMISTRY, 2007, 46 (05) :1655-1664

[9] DETERMINATION OF THE ACIDITY OF LEWIS-ACIDS [J].

LASZLO, P ;

TESTON, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (24) :8750-8754

[10] Coordination sphere flexibility of active-site models for Fe-only hydrogenase: Studies in intra- and intermolecular diatomic ligand exchange [J].

Lyon, EJ ;

Georgakaki, IP ;

Reibenspies, JH ;

Darensbourg, MY .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (14) :3268-3278