Synthesis and Structures of Compounds Containing Double Bonds Between the Heavier Group VA Elements: Diphosphenes, Diarsenes, Phosphaarsenes, And Phosphastibenes

Alan H. Cowley, Jan E. Kilduff, Jon G. Lasch, Sushil K. Mehrotra, Nichlas C. Norman, Marek Pakulski, Bruce R. Whittlesey, Jerry L. Atwood, William E. Hunter

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116 Scopus citations

Abstract

The syntheses of the symmetrical diphosphene (Me3Si)3CP=PC(SiMe3)3 (2), the unsymmetrical diphosphenes [2,4,6-(t-Bu)3C6H2]P=PC(SiMe3)3 (5) and [2,4,6-(i-Bu)3C6H2]P=PCH(SiMe3)2 (7), the phosphaarsene [2,4,6-(ZBu)3C6H2]P=AsCH(SiMe3)2 (12), the phosphastibene [2,4,6-(f-Bu)3C6H2]P==SbCH(SiMe3)2 (14), and the diarsene [2,4,6-(z-Bu)3C6H2] As=AsCH(SiMe3)2 (18) are described. X-ray diffraction studies have been performed on 2,12, and 18. Diphosphene 2 crystallizes in space group Pi (No. 2) with a = 15.629 (7) Å, b = 9.155 (5) Å, c = 12.486 (6) Å, a = 91.58 (4)°, β = 111.42 (5)°, and y = 90.02 (4)°. Phosphaarsene 12 crystallizes in space group PI (No. 2) with a = 9.991 (4) k, b = 10.452 (9) Å, c = 15.140 (15) Å, a = 89.72 (7)°, β = 85.03 (5)°, and y = 77.72 (5)°. Diarsene 18 crystallizes in space group PI (No. 2) with a = 9.955 (9) Å, b = 10.393 (7) Å, c = 15.159 (5) Å, a = 89.56 (4)°, β = 85.39 (6)°, and y = 78.31 (9)°. The nature of the bonding in these and related double-bonded compounds is discussed with use of the available molecular structural and electronic spectral information. An extensive compilation of 31P NMR spectroscopic data is presented and discussed.

Original languageEnglish
Pages (from-to)2582-2593
Number of pages12
JournalInorganic Chemistry
Volume23
Issue number17
DOIs
StatePublished - Aug 1984

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