Trithio-chloro molybdate [MoClS3]-: a versatile precursor for molybdenum trisulfido complexes

The reaction of trithiomolybdate PPh 4] 2MoOS 3] ( 1) with 2 equiv of trimethylchlorosilane generated trithio-chloro molybdate PPh 4]MoClS 3] ( 2) in high yield, by way of a siloxy complex PPh 4]Mo(OSiMe 3)S 3] ( 3). This intriguing reaction provided us with a convenient entry into a series of mononuclear molybdenum trisulfido complexes, PPh 4]MoS 3X] ( 4, X = Cp*; 6a, X = S (t) Bu; 6b, X = SPh; 6c, X = SMes (Mes = mesityl); 6d, X = STip (Tip = 2,4,6-triisopropylphenyl); 6e, X = SDmp (Dmp = 2,6-dimesitylphenyl); 7, X = NPh 2; 8a, X = O (t) Bu; 8b, X = OPh; 8c, X = OC(CH 2) (t) Bu; 8d, X = OC(CH 2)Ph), which were obtained by the reactions of 2 with the corresponding potassium salts. In a similar manner, a citrate complex PPh 4]MoS 3(Me 3cit)] ( 9, Me 3cit = OC(CH 2CO 2Me) 2(CO 2Me)) was synthesized, which may model the molybdenum site of the nitrogenase FeMo-cofactor. The molecular structures of 2, 6c, 7, 8a, 8b, 8c, and 9 were determined by X-ray crystallography.