Disulfido complexes

Scheme 6 Synthesis of platinum disulfido complexes from zerovalent platinum complexes...

Scheme 18 Synthesis of group 5 metal disulfido complexes from the metal thiolato complexes...

Scheme 24 Synthesis of group 6 metal disulfido complexes...

Scheme 31 Synthesis of ruthenium and rhenium disulfido complexes by the use of (TMS)2S as a sulfur reagent...

The insertion reaction of dimethyl acetylenedicarboxylate (DMAD) into the S-S bond of a cyclic disulfido complex of niobium, Nb(S2)(S2CNEt2)3, takes place to give the corresponding dithiolene complex, Nb S2C2(C02Me)2 (S2CNEt2)3 (Scheme 56) [134]. 

Scheme 56 Reaction of niobium and molybdenum disulfido complexes with alkyne...

The dinuclear rhenium disulfido complex with n,rj -S2 ligands (ReCp )2(/U-S2)2 (Cp =7j -C5Me4Et) (type IIa2 complex in Fig. 2) undergoes an insertion reaction of acetylene and ethylene into the S-S bond according to Scheme 57. 

Scheme 59 Reaction of diruthenium disulfido complexes with 1,3-dienes...

Scheme 60 Reaction of a diruthenium disulfido complex with olefins...

Scheme 61 Plausible mechanism for the reaction of diruthenium disulfido complexes with olefins...

Other coordination types for disulfido complexes can be envisioned in addition to those of Table 2. In principle, six electron pairs are available to coordinate to metals... 

The X-ray photoelectron spectra of disulfido complexes have been measured in order to obtain additional information about the effective charge on the sulfur atoms in these ligands. 

Organometallic Cp MoOS(CH2SiMe3) was prepared in 1989 by Faller and Ma (182) by the reaction of the dioxo analogue with H2S. Under similar conditions the methyl derivative produced Cp MoO(S2)(Me), which was readily oxidized to stable Cp MoO(S20)(Me). The formation of the disulfido complex highlights the reactivity of nascent Mo=S bonds. Satisfactory structural characterization of the oxo-thio-complex has not been achieved. 

Fig. 5-25. Separation of various molybdenum disulfido complexes. - Separator column IonPac NS1 (10 pm) eluent 0.002 mol/L TBAOH + 0.001 mol/l Na2C03 / acetonitrile (50 50 v/v) flow rate 1 mL/min detection UV (254 nm) injection volume 50 pL solute concentrations 50 mg/L (NH4)2[Mo2Si2], 50 mg/L [(CH3)4N]2[Mo202S2 (S2)2], and 100 mg/L (NH4)2[Mo3SI3] (taken from [37]).

Mo7022(02)2] - 8H2O ill4e), and [Mo,0022(02),2] - I6H2O (114f). Thus far the diversity in nuclearity apparent in the oxo/peroxomolyb-date series has not been found with the oxo/disulfido complexes. 

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