title: Trithio-chloro molybdate [MoClS3]-: a versatile precursor for molybdenum trisulfido complexes.
abstract: The reaction of trithiomolybdate [PPh 4] 2[MoOS 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.
authors.affiliation: Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Japan.
authors.forename: Jun-ichi
authors.initials: J
authors.lastname: Ito
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Ohki
authors.forename: Masatoshi
authors.initials: M
authors.lastname: Iwata
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Tatsumi
mesh_terms: D018360:Crystallography, X-Ray; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013440:Sulfides / Q000138:chemical synthesis / Q000737:chemistry*; D014297:Trimethylsilyl Compounds / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D013440:Sulfides; D014297:Trimethylsilyl Compounds; C039293:trimethylchlorosilane; D008982:Molybdenum