Coordination Chemistry of the 2-Pyridyldiphosphine Ligands, (py)2P(CH(CH2)3CH)P(py)2 and (py)2P(CH2)2P(py)2 (py

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• 作者：Nathan D. Jones ; Kenneth S. MacFarlane ; Martin B. Smith ; Richard P. Schutte ; Steven J. Rettig ; and Brian R. James
• 刊名：Inorganic Chemistry
• 出版年：1999
• 出版时间：September 6, 1999
• 年：1999
• 卷：38
• 期：18
• 页码：3956 - 3966
• 全文大小：290K
• 年卷期：v.38,no.18(September 6, 1999)
• ISSN：1520-510X

文摘

The synthesis and characterization of a range of Pt(II) and Ru(II) complexes containing the new 2-pyridyldiphosphine ligand, d(py)pcp = (py)₂P(CH(CH₂)₃CH)P(py)₂ (made as a racemate) and the previously reportedd(py)pe = (py)₂P(CH₂)₂P(py)₂ are given (py = 2-pyridyl). The Pt complexes made were cis-PtX₂(d(py)pcp)(X = Cl (1), I (2)), cis-PtX₂(d(py)pe) (X = Cl (3), I (4)), [Pt(d(py)pcp)₂][PF₆]₂ (5), and [Pt(d(py)pe)₂][PF₆]₂ (6);these all contain P,P-bonded diphosphine ligand, as evidenced by ³¹P NMR data and by crystallographic data inthe case of 2 and 3. The X-ray structure of d(py)pe is also reported. The complexes RuX₂(P,P,N-d(py)pcp)(PPh₃)have cis-halogens and a P,P,N-bonding mode of the pyridyldiphosphine (which incorporates a four-memberedP,N-chelate ring) with either a mer-arrangement (in 7a, X = Cl) or a fac-arrangement of the three P donor atoms(in 7b (X = Cl), 8 (X = Br), 9 (X = I)); cis-RuCl₂(dppb)(P,N-PPh₂(py)) (12) (dppb = Ph₂P(CH₂)₄PPh₂) isincluded because it has a donor set corresponding to that in 7b. Use of the purely P,P donor Ph₂P(CH(CH₂)₃CH)PPh₂ (dppcp), made as a racemate, affords trans-RuCl₂(dppcp)₂ (10) and trans-RuCl₂(dppcp)(dppb) (11).Crystallographic data for 7a, 7b, and 12 are reported together with the NMR data for all the Ru complexes.Preliminary results show that the Ru complexes 7b, 8, and 9 are effective precursors for catalytic H₂-hydrogenationof aldimines.