Ambiphilic diphosphine-borane ligands:: Metal→borane interactions within isoelectronic complexes of rhodium, platinum and palladium

被引：146

作者：

Bontemps, Sebastien ^{[2
]}

Sircoglou, Marie ^{[2
]}

Bouhadir, Ghenwa ^{[2
]}

Puschmann, Horst ^{[1
]}

Howard, Judith A. K. ^{[1
]}

Dyer, Philip W. ^{[1
]}

Miqueu, Karinne ^{[3
]}

Bourissou, Didier ^{[2
]}

机构：

[1] Univ Durham, Dept Chem, Durham DH1 3LE, England

[2] Univ Toulouse 3, Equipe Ligands Bifonct & Polymeres Biodegradables, Lab Heterochim Fondamentale & Appl, CNRS,UMR 5069, F-31062 Toulouse 09, France

[3] Univ Pau & Pays Adour, Equipe Chim Phys, IPREM, UMR 5254, F-64013 Pau, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2008年 / 14卷 / 02期

关键词：

ambiphilic ligands; boranes; density functional calculations; transition metals; X-ray diffraction;

D O I：

10.1002/chem.200701027

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Coordination of an ambiphilic diphosphine-borane (DPB) ligand to the RhCI(CO) fragment affords two isomeric complexes. According to X-ray diffraction analysis, each complex adopts a square-pyramidal geometry with trans coordination of the two phosphine buttresses and axial RhB contacts, but the two differ in the relative orientations around the rhodium and boron centres. DFT calculations on the actual complexes provide insight into the influence of the pi-accepting CO co-ligand, compared with previously reported complexes [Rh(mu-Cl)(dpb)](2) and [RhCl(dmap)(dpb)]. In addition, comparison of the (nu) over bar (CO) frequency of [RhCl(CO)(dpb)] with that of the related borane-free complex [RhCl(CO)(iPr(2)PPh)(2)] substantiates the significant electron-withdrawing effect that the sigma-accepting borane moiety exerts on the metal. Valence isoelectronic [PtCl2(dpb)] and [PdCl2(dpb)] complexes have also been prepared and characterized spectroscopically and structurally. The pronounced influence of the transition metal on the magnitude of the M B interaction is highlighted by geometric considerations and NBO analyses.

引用

页码：731 / 740

页数：10

共 121 条

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