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DOI: 10.1039/A706180C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 4499-4502

Reaction of R3PSe with I2; crystal structures of Ph3PSeI2, (Me2N)3PSeI2 and (Et2N)3PSeI2, the first crystallographically characterised charge-transfer complexes of tertiary phosphine selenides with diiodine

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Stephen M. Godfrey, Sheena L. Jackson, Charles A. McAuliffe and Robin G. Pritchard

Abstract

The compounds Ph3PSeI2, (Me2N)3PSeI2 and (Et2N)3PSeI2 have been prepared and characterised by 31P-{H} NMR and infrared spectroscopy. Their single crystal structures have also been determined. Interesting variations in d(P–Se) and d(I–I) are noted upon changing R (Ph, Me2N, Et2N). The variation in d(P–Se) for R3PSeI2 compared to the parent tertiary phosphine selenide is also discussed with respect to the degree of retention of phosphorus selenium double-bond character upon co-ordination of I2. The variations in d(P–Se) and d(I–I) are reflected in the infrared and 31P-{H} NMR spectra of the R3PSeI2 compounds when compared to R3PSe (R = Ph, Me2N or Et2N). The P–Se–I geometries for all three compounds are bent [Ph3PSeI2, 106.0(1), (Me2N)3PSeI2, 100.4(2) (average); (Et2N)3PSeI2, 106.4(1)°] whereas the Se–I–I linkages are all essentially linear [173.69(6), 174.98(8) (average); 178.04(5)°]. These results are interpreted as a donation of electron density from the selenium atom to the σ*-antibonding orbital of the diiodine.

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