Synthesis, Photophysical Properties, and Theoretical Studies of Hydride-Alkynyl Platinum(II) Complexes. Molecular Structures of [trans-PtH(Csrc="http://pubs.acs.org/images/entities/tbd1.gi

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• 作者：Irene Ara ; Jesú ; s R. Berenguer ; Eduardo Eguiz&aacute ; bal ; Juan Fornié ; s ; Julio Gó ; mez ; Elena Lalinde ; and José ; M. S&aacute ; ez-Rocher
• 刊名：Organometallics
• 出版年：2000
• 出版时间：October 16, 2000
• 年：2000
• 卷：19
• 期：21
• 页码：4385 - 4397
• 全文大小：193K
• 年卷期：v.19,no.21(October 16, 2000)
• ISSN：1520-6041

文摘

A series of mononuclear, [trans-PtH(Cs/entities/tbd1.gif">CR)(PPh₃)₂] (R = C₅H₄N-2 (1), (6-Cs/entities/tbd1.gif">CH)C₅H₃N-2(2), C₆H₄NH₂-4 (3), (4-Cs/entities/tbd1.gif">CH)C₆H₄ (4), (CH₂)₅Cs/entities/tbd1.gif">CH (5)), and binuclear, [trans,trans-(PPh₃)₂HPt{s/entities/mgr.gif">-s/gifchars/sigma.gif" BORDER=0 >:s/gifchars/sigma.gif" BORDER=0 >-(Cs/entities/tbd1.gif">C)₂R}PtH(PPh₃)₂] (R = C₅H₃N-2 (7), C₆H₄-1,4 (8)), hydride-alkynyl platinumcomplexes has been prepared in good to moderate yields from the reactions of [trans-PtHCl(PPh₃)₂] with an excess of the corresponding alkyne in the presence of an excess of NEt₂Hand from the reactions of [trans-PtHCl(PPh₃)₂] with 1 equiv of 2 or 4 in the presence ofdiethylamine. An analogous reaction with HCs/entities/tbd1.gif">CCPh₂OH leads to a mixture of [trans-PtH(Cs/entities/tbd1.gif">CCPh₂OH)(PPh₃)₂] (6a) and [Pt(s/gifchars/eta.gif" BORDER=0 >²-HCs/entities/tbd1.gif">CCPh₂OH)(PPh₃)₂] (6b). The binuclear diynecomplex [{(PPh₃)₂Pt}₂{s/entities/mgr.gif">-s/gifchars/eta.gif" BORDER=0 >²:s/gifchars/eta.gif" BORDER=0 >²-(Cs/entities/tbd1.gif">CH)₂C₆H₄-1,4}] (9), prepared in high yield from [Pt(s/gifchars/eta.gif" BORDER=0 >²-C₂H₄)(PPh₃)₂] and HCs/entities/tbd1.gif">CC₆H₄-1,4-Cs/entities/tbd1.gif">CH (0.5 equiv), is also formed in the reaction leadingto 8. Complexes 5, 7, and 8 have been used as precursors to form the mixed-valence Pt(II)-Pt(0) complexes 10-12. The spectroscopic characterization of the complexes and X-ray crystalstructure determination of 1 and 6b are included. Their absorption and some selectedemission spectra, examined on the basis of theoretical studies (EHMO), are also reported.