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• 作者：Laura de Quadras ; Abigail H. Shelton ; Helene Kuhn ; Frank Hampel ; Kirk S. Schanze ; John A. Gladysz
• 刊名：Organometallics
• 出版年：2008
• 出版时间：October 13, 2008
• 年：2008
• 卷：27
• 期：19
• 页码：4979-4991
• 全文大小：523K
• 年卷期：v.27,no.19(October 13, 2008)
• ISSN：1520-6041

文摘

The CuCl-catalyzed reaction of butadiynyl complex trans-(C₆F₅)(Et₃P)₂Pt(CC)₂H (6) and trans-(p-tol)(Et₃P)₂PtCl (7) in HNEt₂ affords trans,trans-(C₆F₅)(Et₃P)₂Pt(CC)₂Pt(PEt₃)₂(p-tol) (8; 62%), but similar reactions of p-tol₃P-substituted coupling partners, or of 6 and trans-(p-tol)(p-tol₃P)₂PtCl (4), are not successful. However, 6 and 4 react under modified conditions (t-BuOK, KPF₆, cat. CuCl, THF/methanol) to give trans,trans-(C₆F₅)(Et₃P)₂Pt(CC)₂Pt(Pp-tol₃)₂(p-tol) (9; 91%). The hexatriynyl complexes trans-(C₆F₅)(R₃P)₂Pt(CC)₃H (R = p-tol, Et) are treated with 4 and 7, respectively, under the original or modified conditions. Workups give trans,trans-(C₆F₅)(R₃P)₂Pt(CC)₃Pt(PR₃)₂(p-tol) (R = p-tol, 12, 40−63%; Et, 17, 59%). The reaction of 6 and ClAu(PPh₃) and KN(SiMe₃)₂ affords trans-(C₆F₅)(Et₃P)₂Pt(CC)₂Au(PPh₃) (18, 97%). The CuCl-catalyzed reaction of (η⁵-C₅H₅)W(CO)₃(CC)₂H and trans-(C₆F₅)(Et₃P)₂PtCl in HNEt₂ generates trans-(C₆F₅)(Et₃P)₂Pt(CC)₂W(CO)₃(η⁵-C₅H₅). The crystal structures of 8, 9, 17, and 18, or solvates thereof, are determined and analyzed in detail. The square-planar end-groups in the C₄ adducts 8 and 9 define angles of 62.3−34.7°, as opposed to ca. 0° in the C₆ adduct 17. Both 9 and 18 exhibit phosphorescence from triplet states concentrated on the C₄ segments. Data with 9 in low-temperature glasses suggest two conformers with different end-group−end-group orientations.