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Syntheses and Structural Characterizations of the Unsymmetrical Diphosphene DmpPPMes* (Dmp = 2,6-Mes₂C₆H₃, Mes* = 2,4,6-^tBu₃C₆H₂) and the Cyclotetraphosphane [DmpPPPh]₂

Supporting Info

Rhett C. Smith,^† Eugenijus Urnezius,^† Kin-Chung Lam,^‡ Arnold L. Rheingold,^‡ and John D. Protasiewicz*^†

Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106-7708, and Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716-2522

Inorg. Chem., 2002, 41 (20), pp 5296–5299

DOI: 10.1021/ic025759l

Publication Date (Web): September 7, 2002

†

Case Western Reserve University.

‡

University of Delaware.

To whom correspondence should be addressed. E-mail: jdp5@ po.cwru.edu.

Abstract

The new diphosphene DmpPPMes* (Dmp = 2,6-Mes₂C₆H₃; Mes* = 2,4,6-^tBu₃C₆H₂, 1) having two different classes of sterically demanding aryls has been prepared and structurally characterized. This structure appears to be the first featuring both types of sterically demanding groups (a meta-terphenyl and Mes*) in a single molecule about a multiply bonded unit. Compound 1 features a PP bond length of 2.024(13) Å. The structure of 1 also allows comparisons to the two previously structurally characterized symmetric diphosphenes DmpPPDmp and Mes*PPMes*. The crystal structure of the cyclotetraphosphane [DmpPPPh]₂ (3), the product of self-dimerization of the unstable diphosphene DmpPPPh (2), has been determined. The structure of 3 demonstrates that a single bulky Dmp group is insufficient to prevent dimerization of 2. ³¹P NMR data for all three compounds are also reported.