Study of the Conformationally Flexible, Wide Bite-Angle Diphosphine 4,6-Bis(3-diisopropylphosphinophenyl)dibenzofuran in Rhodium(I) and Palladium(II) Coordination Complexes

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• 作者：Keying Ding ; Deanna L. Miller ; Victor G. Young ; Jr. ; Connie C. Lu
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：March 21, 2011
• 年：2011
• 卷：50
• 期：6
• 页码：2545-2552
• 全文大小：975K
• 年卷期：v.50,no.6(March 21, 2011)
• ISSN：1520-510X

文摘

The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as ^iPrDPDBFphos) was prepared and studied for its potential as a trans-chelating ligand in transition-metal coordination complexes. In the rhodium norbornadiene complex [(^iPrDPDBFphos)Rh(NBD)]BF₄, which has been characterized with multinuclear NMR spectroscopy, X-ray crystallography, and electrochemical studies, the ligand binds in cis fashion. In the bis(acetonitrile) complexes of rhodium and palladium [(^iPrDPDBFphos)M(CH₃CN)₂](BF₄)_n (M = Rh, Pd; n = 1, 2), the ligand adopts a trans coordination geometry. Density functional theory (DFT, M06-L) calculations predict that the trans conformer is energetically more favorable than the cis by 3.5 kcal/mol. Cyclic voltammograms of the bis(acetonitrile) Pd(II) and Rh(I) complexes contain reversible and quasi-reversible reduction events, respectively, which are preliminarily assigned as metal-based redox reactions.