Neutral and cationic complexes with P-bonded 2-pyridylphosphines as N-donor ligands toward rhodium.: Electrical charge vs steric hindrance on the conformational control

被引：19

作者：

Casares, Juan A. ^{[1
]}

Espinet, Pablo ^{[1
]}

Martin-Alvarez, Jose M. ^{[1
]}

Santos, Veronica ^{[1
]}

机构：

[1] Univ Valladolid, Fac Ciencias, E-47071 Valladolid, Spain

来源：

INORGANIC CHEMISTRY | 2006年 / 45卷 / 17期

关键词：

D O I：

10.1021/ic0600477

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Bimetallic palladium(II)-rhodium(I) and gold(I)-rhodium(I) complexes of the type [(4,4'-Me-2-bipy)(C6F5)Pd(mu-PPh3-n-Py-n)Rh(diene)](BF4)(2) and [(C6F5)Au(mu-PPh3-nPyn)Rh(diene)](BF4) (n = 2, 3; Py = 2-pyridyl) have been synthesized. The P donor atom of the bridging ligands (mu-PPh3-nPyn) is coordinated to the Pd or to the Au center. The resulting complexes react with [Rh(diolefin)(solv)(2)](+) (solv = acetone) in a way similar to pyrazolylborates, affording square-planar or pentacoordinated rhodium complexes with two or the three N-donor ends chelating the Rh atom. The metallacycles formed upon chelation can adopt one of two conformations in the square-planar Rh(I) complexes, either bringing the other metal close to the Rh center or bringing it to a remote position. The first conformation is preferred for the gold P-coordinated complexes and the second for the palladium complexes. The X-ray structures of [(4,4'-Me-2-bipy)](C6F5)Pd(mu-PPhPy2)Rh(COD)](BF4)(2) (COD = 1,5 cyclooctadiene) and [Au(C6F5)(mu-PPhPy2)Rh(TFB)](BF4) (TFB = 5,6,7,8-tetrafuoro-1,4-dihydro-1,4-etenonaphthalene) are reported.

引用

页码：6628 / 6636

页数：9

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