Sellmann, Dieter; Binker, Gerhard; Schwarz, Joerg; Knoch, Falk; Boese, Roland; Huttner, Gottfried; Zsolnai, Laszlo:

Transition metal complexes with sulfur ligands. XXIX. Redox coupled sulfur ligand transfer reactions between iron and molybdenum centers: synthesis, structure and reactivity of [m-dttd[Mo(CO)3]2].2H2O and [m-dttd[Mo(CO)4]2]2- [dttd2- = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(-2)].

In: Journal of Organometallic Chemistry, Jg. 323 (1987) ; Nr. 3, S. 323-338
ISSN: 0022-328X
Zeitschriftenaufsatz / Fach: Chemie
The reaction of [Fe(dttd)(THF)2] (I; H2dttd = 2,3,8,9-dibenzo-1,4,7.10-tetrathiadecane) with [Mo(CO)4(nor)] (II; nor = norbornadiene) gave [m-dttd{Mo(CO)3}2] (III) by way of a redox coupled ligand transfer. The reaction proceeds by transferring the dttd2- ligand from I to II, giving [m-dttd{Mo(CO)4}2]2- (IV) which is subsequently oxidized by FeII to give III. Redn. of III by LiBEt3H/CO regenerates IV. In III both Mo centers are connected in 3 different ways, viz., by a Mo-Mo bond, thiolate S atoms of dttd2-, and the clamp of the SCH2CH2S bridge. The latter preserves the binuclearity when the closed II is reduced to the open IV. The reaction of Li2[m-dttd{Mo(CO)3}2] with NOPF6 yields [m-dttd{Mo(CO)3(NO)}2]. The structures of III, (NMe4)2[m-dttd{Mo(CO)4}2] and (NMe4)[Mo(CO)4(MeSC6H4S)] were detd. from x-ray diffraction studies.