Syntheses and Theoretical and Mechanistic Aspects of 1-Thia-24- and 1-Thia-34-disphosphole Formed from CS2 and tBuCP and Crystal and Molecular Structure of the First 1-Thia-34-disphosphole Complex: cis-[\{PtCl2(PEt3)\}2(P2SC2tBu2)]

D'Arbeloff-Wilson, Sarah E, Hitchcock, Peter B, Krill, Steffen, Nixon, John F, Nyulászi, Laszlo and Regitz, Manfred (2000) Syntheses and Theoretical and Mechanistic Aspects of 1-Thia-24- and 1-Thia-34-disphosphole Formed from CS2 and tBuCP and Crystal and Molecular Structure of the First 1-Thia-34-disphosphole Complex: cis-[\{PtCl2(PEt3)\}2(P2SC2tBu2)]. Journal of the American Chemical Society, 122. 4557 - 4562. ISSN 0002-7863

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Abstract

The reaction of tBuCP with CS2 (or its ylide type complexes such as R3PCS2 (R = Et, Ph, cyclohexyl), (C5H10N)2CCS2, or (C4H8NO)2CCS2) gives a mixture of 3,5-di-tert-butyl-1-thia-2,4-diphosphole and 2,5-di-tert-butyl-1-thia-3,4-diphosphole, which were characterized by NMR spectroscopy. The latter was also characterized by the single-crystal X-ray structure determination of its bis(platinum(II)) complex [(PtCl2PEt3)2(μ-P2SC2tBu2)]. This is the first structural characterization of a 1-thia-3,4-diphosphole ring. The mechanism of these reactions was explored by B3LYP/6-311+G** level quantum chemical calculations. The reaction pathway involves a phosphadithiolediylcarbene and its diphosphatetrathiafulvalene dimer as intermediates. Several other possible reaction pathways were ruled out.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: John Nixon
Date Deposited: 06 Feb 2012 19:55
Last Modified: 11 Jun 2013 11:30
URI: http://sro.sussex.ac.uk/id/eprint/22954
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