Binuclear phosphinothioylidene complexes

Article abstract of DOI:10.1021/om50004a030

Lawesson's reagent (the dimer of (p-methoxyphenyl)thionophosphine sulfide) reacts with dicyclopentadienyltetracarbonyldimolybdenum or -ditungsten to give binuclear complexes containing a phosphinothioylidene ligand. These complexes were characterized on the basis of analytical and spectral data and a single-crystal X-ray analysis of the molybdenum complex. Crystal data of [(C₅H₅)₂Mo₂(CO) ₄(SP-C₆H₄OCH₃)] are as follows: a = 9.471 (4) ?, b = 9.119 (3) ?, c = 16.145 (2) ?, α = 90.75 (2)°, β = 97.37 (2)°, γ = 126.89 (3)°, V = 1098.8 ?,³ Z = 2, triclinic, space group P1. Intensity data were collected by counter methods, Mo Kα₁ radiation. The structure was refined on 3541 reflections with I > 2.30σ(I) to R_F = 0.020 and R_wF = 0.028. The P atom is σ bonded to Mo(1) and P=S π bonded to Mo(2): Mo-Mo = 3.245 (1) ?, Mo(1)-P = 2.326 (1) ?, Mo(2)-P = 2.451 (1) ?, Mo(2)-S = 2.567(1) ?, P=S = 2.022 (1) ?, Mo(1)-P-Mo(2) = 85.53 (3)°. One carbonyl attached to Mo(2) is semibridging: Mo(2)-C(21) = 1.968 (3) ?, Mo(1)?C(21) = 2.864 (3) ?, Mo(2)-C(21)-O(21) = 166.0 (2)°.