412010-42-5Relevant articles and documents
Molybdenum and tungsten complexes of sulfene (thioformaldehyde S,S-dioxide)
Schenk, Wolfdieter A.,Nielsen, Katja,Burzlaff, Nicolai I.,Hagel, Michael
, p. 1079 - 1085 (2008/10/08)
Propionitrile complexes fac-[M(CO)3(P-P)(NCEt)] (M = Mo (3), W (4); P-P = Ph2PCH2PPh2 (a), Ph2PC2H4PPh2 (b), Ph2PC3H6PPh2 (c), (S,S)-Ph2PCHMeCHMePPh2 (d), Fe(C5H4PPh2)2 (e)) were synthesized from [M(CO)3(NCEt)3] and the corresponding diphosphine. Reactions of 3 and 4 with sulfur dioxide initially gave complexes fac-[M(CO)3-(P-P)(η2-SO2)] (M = Mo (5), W (6)), which slowly isomerized to mer-[M(CO)3(P-P)(η1-SO2)] (M = Mo (7), W (8)). The structures of 7b and 8b were determined by X-ray crystallography. Both compounds are isostructural (monoclinic, space group P21/n (No. 14)) with almost identical unit cell dimensions (7b, a = 14.511(5) A, b = 12.797(2) A, c = 16.476(6) A, β = 115.92(2)°; 8b, a = 14.478(8) A, b = 12.794(3) A, c = 16.442(9) A, β = 116.01(2)°) and molecular geometries. Treatment of either fac-[M(CO)3(P-P)(η2-SO2)] or mer-[M(CO)3(P-P)(η1-SO2)] with diazomethane yielded the sulfene complexes mer-[M(CO)3(P-P)(η2-CH2SO2)] (M = Mo (9), W (10)). The structure of 10a was determined crystallographically: monoclinic, space group P21/n (No. 14), a = 11.719(2) A, b = 17.392(4) A, c = 13.441(3) A, β = 95.58(2)°. The tungsten atom resides in the center of a distorted pentagonal bipyramid. The sulfene ligand occupies two adjacent equatorial sites with the bond distances W-C, 2.322(13) A, W-S, 2.353(3) A, and S-C, 1.721(12) A. The latter equals the S-C single bond distance in thiirane S,S-dioxide, indicating a high degree of charge density transfer into the LUMO of the sulfene ligand.