A conformational study of phospha(III)- and phospha(V)-guanidine compounds.
Spectroscopic, crystallographic, and computational studies of the substituent distribution about the "NCN" unit in a series of phospha(III)- and phospha(V)-guanidines, R(2)PC{NR'}{NHR'} and R(2)P(E)C{NR'}{NHR'} (R = Ph, Cy; R' = (i)Pr, Cy; E = S, Se), are reported. In the phosphorus(III) systems, the P-diphenyl substituted compounds are observed as only one isomer, shown by NMR spectroscopy to be the E(syn)-(alpha) configuration. In contrast, the corresponding P-dicyclohexyl derivatives exist as a mixture of E(syn)-(alpha) and Z(anti) in solution. Spectroscopic techniques are unable to determine whether the latter isomer exists as the alpha- or beta-conformer relative to rotation about the P-C(amidine)() bond; however, DFT calculations indicate a low-energy structure for the N,N'-dimethyl model complex in the beta-conformation. In their oxidized sulfo and seleno forms, the P-diphenyl compounds are present as an interconverting equilibrium mixture of the E(syn)-(beta) and Z(syn)-(beta) isomers in solution ( approximately 3:2 ratio), whereas for the P-dicyclohexyl analogues, the latter configuration (in which the nitrogen substituents are in a more sterically unfavorably cisoid arrangement about the imine double bond) is the dominant form. Intramolecular E...HN (E = S, Se) interactions are observed in solution for the Z(syn)-(beta) configuration of both P-substituted species, characterized by J(SeH) coupling in the NMR spectrum for the P(V)-seleno compounds and a bathochromic shift of the NH absorption in the infrared spectrum. An X-ray crystallographic analysis of representative Ph(2)P(E)- and Cy(2)P(E)-substituted species shows exclusively the E(syn)-(beta) configuration for the P-diphenyl substituted compounds and the Z(syn)-(beta) form for the P-dicyclohexyl derivatives, independent of the chalcogen and the nitrogen substituents. Results from a DFT analysis of model compounds fail to identify a compelling electronic argument for the observed preferences in substituent orientation, suggesting that steric factors play an important role in determining the subtle energetic differences at work in these systems.
Mansfield
Natalie E
NE
Department of Chemistry, University of Sussex, Falmer, Brighton BN1 9QJ, UK.
Grundy
Joanna
J
Coles
Martyn P
MP
Avent
Anthony G
AG
Hitchcock
Peter B
PB