UEBERGANGSMETALLKOMPLEXE MIT SCHWEFELLIGANDEN. X. SUBSTITUTIONS- UND REDOX-REAKTIONEN VON MOLYBDAEN(0)-CARBONYL-KOMPLEXEN MIT DEN MEHRZAEHNIGEN THIOETHER-THIOL-LIGANDEN 1,2-METHYLTHIOBENZOLTHIOL, 1,4,7-TRITHIAHEPTAN, 2,3,8,9-DIBENZO-1,4,7,10-TETRATHIADECAN SOWIE 1,2-BENZOLDITHIOL

Article abstract of DOI:10.1016/0022-328X(85)88027-X

During a study of the reactions of molybdenum(0) carbonyl complexes with multidentate organosulfur ligands, (NMe4)2 was obtained from and (NMe4)2(SC2H4SC2H4S); subsequent alkylation with 1,2-dibromoethane gave (TTCN=1,4,7-trithiacyclononane).TTCN, which up to now had been obtained only with difficulty, is liberated from by (NMe4)2(SC2H4SC2H4S) under regeneration of the starting complex (NMe4)2.TTCN and yield . and (NMe4)2(dttd), (dttd^2-=2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(-2)), give (NMe4)2<μ-dttd2>, which reacts to form a Mo(CO)3 species under heating; further CO substitution is not observed.Treatment of with C6H4(SH)2 and CH3SC6H4SH, respectively, leads via redox reactions to the molybdenum(II) complexes and .Under normal conditions, these complexes show no substitution of PPh3 by C6H4S2^2- or CH3SC6H4S^-; however, under thermally more vigorous conditions in refluxing methoxyethanol, and Na2(C6H4S2) yield IV(C6H4S2)3>^2- in a redox reaction; the anion is isolated as (NMe4)2. and CH3SC6H4SH yield, at room temperature, the binuclear ; with Na/THF, it leads to ^-, with PPh3 to , and with CH3SC6H4S^- to ^- as well as to ^-, which are isolated as NMe4⁺ salts.In (NMe4), apart from one CO, only sulfur is coordinated to the Mo center; its CO ligand shows an extremely low IR absorption at 1775 cm^-1, indicating high electron density at the Mo center.Photochenmical substitution of CO by N2 was not possible either with this CO or with the other CO complexes.