Phosphinsubstituierte Chelatliganden, XIV [1]. Wasserstoff-Brückenbindung in THF-Addukten von Tetracarbonylchrom-und -molybdänkomplexen mit P,S-koordinierten Phosphinothioformamid-Liganden. Kristallstruktur von [(CO)4Cr(PPh2C(S)NHMe)] · THF Phosphine-Substituted Chelate Ligands, XIV [1]. Hydrogen Bonding in THF-Adducts of Tetracarbonylchromium and -molybdenum Complexes with P,S-Coordinated Phosphinothioformamide Ligands. Crystal Structure of [(CO)4Cr(PPh2C(S)NHMe)] · THF

Abstract

The tetracarbonyl chromium and molybdenum P,S-chelate complexes 1a, b and 2a, b are obtained by low-temperature photolysis of the metal hexacarbonyls with the neutral phosphinothioformamide ligands, Ph2PC(S)NHR (R = Me (a). Ph (b)), as stoichiometric 1/1 IHF adducts. A weak N-H···O(THF) hydrogen bond is deduced from the 1H NMR spectra which show a collapse of the N-methyl doublet in la (Tc -18 °C) but not in 2a. Unusually small P-C(S) couplings are observed in the 13C{1H} NMR spectra. The N-methyl chromium complex la crystal­lizes in the triclinic space group P1 (Z = 2) with the lattice constants a = 1076.6(3), b = 1235.8(3), c = 915.1(3) pm, α = 97.99(4)°, β = 92.73(5)°, γ = 87.63(5)°. The planar thioamide unit adopts the Z configuration and is linked to the tetrahydrofuran molecule by a hydrogen bond (N-H1-O31 164°) with an O···H contact distance of 191 pm.