Boone Michael P, Stephan Douglas W
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 (Canada).
Chemistry. 2014 Mar 17;20(12):3333-41. doi: 10.1002/chem.201304289. Epub 2014 Feb 25.
The reactivity of [{(Ph2 PC6 H4 )2 B(η(6) -Ph)}RuCl][B(C6 F5 )4 ] (1) as a Lewis acid was investigated. Treatment of 1 with mono and multidentate phosphorus Lewis bases afforded the Lewis acid-base adducts with the ortho-carbon atom of the coordinated arene ring. Similar reactivity was observed upon treatment with N-heterocyclic carbenes; however, adduct formation occurred at both ortho- and para-carbon atoms of the bound arene with the para-position being favoured by increased steric demands. Interestingly treatment with isocyanides resulted in adduct formation with the B-centre of the ligand framework. The hydride-cation [{(Ph2 PC6 H4 )2 B(η(6) -Ph)}RuH] [B(C6 F5 )4 ] was prepared via reaction of 1 with silane. This species in the presence of a bulky phosphine behaves as a frustrated Lewis pair (FLP) to activate H2 between the phosphorus centre and the ortho-carbon atom of the η(6) -arene ring.
研究了[{(Ph₂PC₆H₄)₂B(η⁶-Ph)}RuCl][B(C₆F₅)₄](1)作为路易斯酸的反应活性。用单齿和多齿磷路易斯碱处理1,得到与配位芳烃环的邻位碳原子形成的路易斯酸碱加合物。用N-杂环卡宾处理时观察到类似的反应活性;然而,加合物的形成发生在键合芳烃的邻位和对位碳原子上,随着空间需求的增加,对位更受青睐。有趣的是,用异腈处理导致与配体骨架的B中心形成加合物。通过1与硅烷反应制备了氢化物阳离子[{(Ph₂PC₆H₄)₂B(η⁶-Ph)}RuH][B(C₆F₅)₄]。在大位阻膦存在下,该物种表现为受阻路易斯对(FLP),以活化磷中心和η⁶-芳烃环的邻位碳原子之间的H₂。