Spectroscopic Properties and Electronic Structure of the Cycloheptatrienyl Molybdenum Alkynyl Complexes [Mo(C≡CR)(Ph2PCH2CH2PPh2)(η-C7

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• 作者：Neil J. Brown ; David Collison ; Ruth Edge ; Emma C. Fitzgerald ; Madeleine Helliwell ; Judith A. K. Howard ; Hannah N. Lancashire ; Paul J. Low ; Joseph J. W. McDouall ; James Raftery ; Charlene A. Smith ; Dmit
• 刊名：Organometallics
• 出版年：2010
• 出版时间：March 8, 2010
• 年：2010
• 卷：29
• 期：5
• 页码：1261-1276
• 全文大小：1302K
• 年卷期：v.29,no.5(March 8, 2010)
• ISSN：1520-6041

文摘

A series of molybdenum alkynyl complexes [Mo(C≡CR)(dppe)(η-C₇H₇)] featuring a range of alkynyl substituents R with varying electron-donating and -withdrawing properties have been prepared. Oxidation of representative members of the series to the corresponding 17-electron radical cations has been achieved through both chemical oxidation and in situ spectroelectrochemical methods. The largely metal-centered character of the HOMO in this class of compounds has been established through a combination of experimental measurements (IR, UV−vis−NIR, EPR spectroscopies) and DFT-based calculations and rationalized in terms of the stabilization of the metal d_xy, d_yz, d_xz, and d_x²-y² through π- and δ-interactions with the C₇H₇ ring and concomitant destablization of the d_z² orbital.