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Conformational Isomerism and Chlorotropy Mechanisms of Chloromethyl- and Trichloromethyldichlorophosphines

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Abstract

35Cl NQR spectroscopy and MP2//RHF/6-31++G(d,p) and MNDO-PM3 calculations were used to study the conformational and chlorotropic isomerism of chlorodimethyldichlorophosphine (I) and trichloromethyldichlorophosphine (II). The experimental 35Cl NQR spectrum is in complete accord with the staggered conformation of phosphine II obtained using an RHF/6-31++G(d,p) calculation. The rotational barrier of the CCl3 group is 38.1 kJ/mol. On the other hand, the spectrum of phosphine I is in accord with a gauche conformation, which agrees with experiment only upon taking account of electron correlation (MP2). The ylide and phosphinic chlorotropic isomers for I and II are thermodynamically stable with greater stability found for II. The chlorotropic phosphine–ylide conversion in system I proceeds exclusively through a sigmatropic transition state in qualitative accord with nonempirical and semiempirical calculations. Such a conversion is theoretically possible in system II by means of dissociation of the P+—C− ylide bond.

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Authors and Affiliations

  1. Institute of Bioorganic and Petroleum Chemistry, National Academy of Sciences of Ukraine, 1 Murmans'ka Vul., 02094, Kyiv, Ukraine

    E. A. Romanenko & A. M. Nesterenko

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  1. E. A. Romanenko
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  2. A. M. Nesterenko
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Romanenko, E.A., Nesterenko, A.M. Conformational Isomerism and Chlorotropy Mechanisms of Chloromethyl- and Trichloromethyldichlorophosphines. Theoretical and Experimental Chemistry 37, 163–167 (2001). https://doi.org/10.1023/A:1011976120607

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