ISSN:
0009-2940
Keywords:
1,1-Dithiolate
;
Rhenium
;
Carbonyl complexes
;
Bridging ligands
;
Bimetallic complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of fac-[Re(CO)3(S2CPR3)Br] with [Rc(CO)5]- affords the dinuclear octacarbonyl compounds [Re2(CO)8(μ-S2CPR3)] (3a—b), which have been isolated and characterized by spectroscopic methods. An X-ray crystal-structure determination of the derivative 3a (R=Cy) shows that the S2CPCY3 ligand acts as an η1(S);η1(S′) bridge donating two electrons to each metal atom of a symmetrical (CO)4Re—Re(CO)4 unit. This unit is presumably formed through a concerted process involving carbonyl/sulfur exchange in the nonsymmetrical octacarbonyl (CO)3(S2CPR3)Re—Re(CO)5 generated after the coupling of the bromo derivative with the carbonyl anion. Complexes 3a—b can be obtained more directly by adding S2CPR3 to [Re2(CO)8(μ-H)(μ-CH=CHnBu)], which is formed by irradiation of Re2(CO)10 with 1-hexene. Hydride addition to the central carbon atom of the S2CPR3 ligand of 3a-b occurs with loss of PR3, to give the anion [Re2(CO)8(μ-S2CH)]- which may be isolated as a salt with the PPN+ cation. The octacarbonyl compounds 3a-b can be converted into hexacarbonyl complexes [Re2(CO)6(μ-S2CPR3)] (5a-b) by heating in toluene or octane at reflux temperature. According to an X-ray crystal-structure determination of the derivative 5a (R=Cy), the loss of one carbonyl ligand from each rhenium atom is accompanied by the rearrangement of the S2CPR3 ligand which changes its bonding mode from η1(S);η1(S′) donating four electrons to η3(S,C,S′);η2(S,S′) donating eight electrons.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971301025
