Phenylmercury(II) derivatives of tetraorganodichalcogenoimidodiphosphorus acids. Crystal and molecular structure of PhHg{(OPR2)(SPPh2)N} (2) (R = Me, Ph)

Bumbu, O., Silvestru, A., Silvestru, C., Drake, J. E., Hursthouse, M. B. and Light, M. E. (2003) Phenylmercury(II) derivatives of tetraorganodichalcogenoimidodiphosphorus acids. Crystal and molecular structure of PhHg{(OPR2)(SPPh2)N} (2) (R = Me, Ph). Journal of Organometallic Chemistry, 687 (1), 118-124. (doi:10.1016/j.jorganchem.2003.07.016).

Abstract

The reactions between PhHgCl or PhHgAc and M[(XPR2)(YPR2')N] (M = Na, K; X, Y = O, S; R, R' = Me, Ph, OEt), in 1:1 molar ratio, have been investigated. PhHg[(XPR2)(YPR2')N] derivatives were isolated as microcrystalline powders and were characterised using IR and NMR (H-1, C-13 and P-31) spectroscopy and mass spectrometry. The molecular structure of PhHg[(OPR2)(SPPh2)N] [R = Me (1), Ph (2)] was investigated by X-ray diffraction. In the monomeric unit, PhHg[(OPR2)(SPPh2)N], the mercury atom forms the primary bonds with the carbon of the phenyl group and the sulfur atom of the phosphorus ligand [Hg(1)-S(1) 2.405(1) Angstrom for 1, 2.398(2) Angstrom for 2]. These primary bonds are significantly deviated from the expected linear arrangement [C(1)-Hg(1)-S(1) 166.4(2)degrees for 1, 165.0(2)degrees for 2]. Both compounds exhibit dimeric associations in the crystal through S,O-bridging organophosphorus ligands [Hg(1)-O(1) 2.556(4) Angstrom for 1, 2.588(4) Angstrom for 2], thus resulting in a distorted T-shaped arrangement of the CHgSO coordination core.. The formation of a 12-membered Hg2O2S2P4N2 ring with different conformation in 1 and 2, respectively, results in different additional chalcogen atoms being in the proximity of the metal atom. Weak transannular (HgO)-O-... [2.753(4) Angstrom] are also established in 1, leading to a tricyclic ladder structure with a planar central Hg2O2 ring.

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Contributors

Author: M. E. Light

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