Neutral and Cationic Complexes with P-Bonded 2-Pyridylphosphines as N-Donor Ligands toward Rhodium. Electrical Charge vs Steric Hindrance on the Conformational Control
详细信息 查看全文
- 作者：Juan A. Casares ; Pablo Espinet ; José ; M. Martí ; n-Á ; lvarez ; Veró ; nica Santos
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：August 21, 2006
- 年：2006
- 卷：45
- 期：17
- 页码：6628 - 6636
- 全文大小：236K
- 年卷期：v.45,no.17(August 21, 2006)
- ISSN：1520-510X
文摘
Bimetallic palladium(II)-rhodium(I) and gold(I)-rhodium(I) complexes of the type [(4,4'-Me2-bipy)(C6F5)Pd(
-PPh3-nPyn)Rh(diene)](BF4)2 and [(C6F5)Au(-PPh3-nPyn)Rh(diene)](BF4) (n = 2, 3; Py = 2-pyridyl) have been synthesized.The P donor atom of the bridging ligands (-PPh3-nPyn) is coordinated to the Pd or to the Au center. The resultingcomplexes 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. Themetallacycles 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 ispreferred for the gold P-coordinated complexes and the second for the palladium complexes. The X-ray structuresof [(4,4'-Me2-bipy)](C6F5)Pd(-PPhPy2)Rh(COD)](BF4)2 (COD = 1,5 cyclooctadiene) and [Au(C6F5)(-PPhPy2)Rh(TFB)](BF4) (TFB = 5,6,7,8-tetrafuoro-1,4-dihydro-1,4-etenonaphthalene) are reported.
-PPh3-nPyn)Rh(diene)](BF4)2 and [(C6F5)Au(-PPh3-nPyn)Rh(diene)](BF4) (n = 2, 3; Py = 2-pyridyl) have been synthesized.The P donor atom of the bridging ligands (-PPh3-nPyn) is coordinated to the Pd or to the Au center. The resultingcomplexes 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. Themetallacycles 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 ispreferred for the gold P-coordinated complexes and the second for the palladium complexes. The X-ray structuresof [(4,4'-Me2-bipy)](C6F5)Pd(-PPhPy2)Rh(COD)](BF4)2 (COD = 1,5 cyclooctadiene) and [Au(C6F5)(-PPhPy2)Rh(TFB)](BF4) (TFB = 5,6,7,8-tetrafuoro-1,4-dihydro-1,4-etenonaphthalene) are reported.