Diruthenium(III,III) Bis(alkynyl) Compounds with Donor/Acceptor-Substituted geminal-Diethynylethene Ligands

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• 作者：William P. Forrest ; Zhi Cao ; Kerry M. Hassell ; Boone M. Prentice ; Phillip E. Fanwick ; Tong Ren
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：March 5, 2012
• 年：2012
• 卷：51
• 期：5
• 页码：3261-3269
• 全文大小：450K
• 年卷期：v.51,no.5(March 5, 2012)
• ISSN：1520-510X

文摘

Reported in this contribution are the preparation and characterization of a series of Ru<sub>2sub>(DMBA)<sub>4sub> (DMBA = N,N鈥?dimethylbenzamidinate) bis(alkynyl) compounds, trans-Ru<sub>2sub>(DMBA)<sub>4sub>(X-gem-DEE)<sub>2sub> [gem-DEE = 蟽-geminal-diethynylethene; X = H (1), Si<sup>isup>Pr<sub>3sub> (2), Fc (3); 4-C<sub>6sub>H<sub>4sub>NO<sub>2sub> (4), and 4-C<sub>6sub>H<sub>4sub>NMe<sub>2sub> (5)]. Compounds 1鈥?b>5 were characterized by spectroscopic and voltammetric techniques as well as the single-crystal X-ray diffraction studies of 2 and 3. Both the single-crystal structural data of compounds 2 and 3 and the spectroscopic/voltammetric data indicate that the gem-DEE ligands are similar to simple acetylides in their impact on the molecular and electronic structures of the Ru<sub>2sub>(DMBA)<sub>4sub> core. Furthermore, density functional theory calculations revealed more extensive 蟺 delocalization in aryl-donor-substituted gem-DEEs and that the hole-transfer mechanism will likely dominate the charge delocalization in Ru<sub>2sub>-gem-DEE-based wires.