Nouveaux complexes à enchaînement GeRuGe: les bis(dimethylgermyl)alcane ruthenium tetracarbonyles. I. Synthèse et réactions de clivage
作者:Jacques Barrau、Najib Ben Hamida、Jacques Satgé
DOI:10.1016/0022-328x(90)85259-2
日期:1990.9
Bis(dimethylgermyl)alkane ruthenium tetracarbonyls Me2Ge(CH2)nGe(Me2)Ru(CO)4 (n = 1, 2) are obtained by reaction of bis(dimethylgermyl)alkanes Me2(H)Ge(CH2)nGe(H)Me2 (n = 1, 2) with Ru3(CO)12 under UV irradiation, or by heating. Various CO substitution reactions with phosphines by heating and cleavage reactions with protonic, electrophilic, nucleophilic or radical reagents are described. XO oxides
The ruthenacyclic carbamoyl complexes [Ru (2-NHC(O)C5H4N) (CO)2(X) (NCMe)] (X = Cl, Br) (1) and [Ru (2-NHC(O)C5H4N) (CO)2 (2-S-Py)] (2) undergo substitution reactions with organophosphines to afford derivatives which are prone to a redistribution of the phosphine ligand. We have studied these redistribution reactions experimentally and computationally, and proposed an essentially common reaction pathway
钌环氨基甲酰基络合物[Ru(2-NHC(O)C 5 H 4 N)(CO)2(X)(NCMe)](X = Cl,Br)(1)和[Ru(2-NHC(O) C 5 H 4 N)(CO)2(2-S-Py)](2)与有机膦发生取代反应,得到易于重新分配膦配体的衍生物。我们已经通过实验和计算方法研究了这些再分布反应,并提出了一个基本的通用反应途径。结果表明氨基甲酰基配体发挥非常强的反式作用。
Structural Mimics of the [Fe]-Hydrogenase: A Complete Set for Group VIII Metals
A set of structural mimics of the [Fe]-hydrogenase active site comprising all the groupVIIImetals, viz., [M(2-NHC(O)C5H4N)(CO)2(2-S-C5H4N)], has been synthesized. They exist as a mixture of isomers in solution, and the relative stability of the isomers depends on the nature of the metal and the substituent at the 6-position of the pyridine ligand.
一组[Fe]-加氢酶活性位点的结构模拟物,包括所有第VIII组金属,即[M(2-NHC(O)C 5 H 4 N)(CO)2(2-SC 5 H 4 N)],已经合成。它们以异构体的混合物形式存在于溶液中,异构体的相对稳定性取决于金属的性质和吡啶配体6位上的取代基。