Reaction of a complexed phosphinidene with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene |
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Authors: | Vlaar M J Ehlers A W Schakel M Clendenning S B Nixon J F Lutz M Spek A L Lammertsma K |
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Institution: | Department of Organic and Inorganic Chemistry, Faculty of Sciences, Vrije Universiteit, Amsterdam, The Netherlands. |
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Abstract: | The terminal phosphinidene complex PhPW(CO)5 reacts with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene to give two unexpected multicyclic organophosphorus compounds. One of them results from an initial 1,2-addition, followed by an intramolecular rearrangement. B3LYP/6-31G* calculations on simplified parent systems suggest that the reaction follows a unique concerted reaction pathway. The second, and major, product is a tetraphosphaquadricyclane derivative, which presumably results from an intramolecular 2+2] cycloaddition of an intermediate tetraphosphanorbornadiene complex. Single-crystal X-ray structures are presented for both products. |
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