Chalcogen thiolate

Like the three-coordinate aluminum and gallium alkoxides, the corresponding thiolates, selenolates, and tellurolates require very bulky substituents at the chalcogen atom to ensure a low metal coordination number. In addition, the steric requirements associated with the preservation of the low coordination number at the metal are increased by the longer M—S and M—Se bond lengths. The ten examples of low-coordinate,... 

Gallium-chalcogen clusters (Cp Gali)4 (E = S, Se) result from the reaction of (Me3Si)2E with Cp GaCl2, while the P—N heterocycle (8) can be thiolated at P(V) using (Me3Si)2S (equation 25)45. 

The oxidative addition of chalcogen-chalcogen bonds in RE—ER is widely applied in transition metal chemistry and is often a useful route for the preparation of thiolates, selenolates and, to a more limited extent, tellurolates. The oxidative addition of X2 = HO—OH and PhC(0)0—0C(0)Ph is also known and, in the case of Ptu complexes, gives predominantly trans products 47... 

Much of this work has been directed towards materials-based applications, as volatile compounds might be CVD precursors see Chemical Vapor Deposition) and the ability of the thiolates and their fellows to react with the free chalcogens may assist doping lanthanide ions into optical and electrical materials. Thus, thermolysis of the [Ln(SePh)3(thf)3] (Ln =... 

The reaction of a polar organometallic compound with elemental sulfur, selenium or tellurium gives a thiolate, selenolate or tellurolate, respectively [60, 61] in many syntheses, however, further reactions are carried out with the intermediary chalcogenates , e.g. alkylations ... 

Within this context, the present article concentrates on transition metal cluster complexes of cobalt, iron and manganese with mixed chalcogen/carbonyl ligand spheres obtained by reaction of simple binary metal carbonyls with alkali-metal sulfides, alkali-metal thiolates or transition-metal thiolate complexes and their selenium or tellurium counterparts. 

A large fraction of the binuclear mixed chalcogen/carbonyl transition metal complexes of iron and manganese contain the M2E (CO)6 core with the butterfly-type structure (n = 2) or substructure (n — 3, see Section 1.10.3). As an example of a complex with thiolate ligands, the structure of [Fe2(SC3H7)2(CO)6] is shown in... 

A hexanuclear chalcogen/carbonyl compound of cobalt containing no thiolate ligands, [Co6E2(E2)(CO)i4] (E = S, Se), is shown in Fig. 27 for E = The cluster complex is assembled from two identical trinuclear Co3S(CO)vS2 sub-units which share the S atoms of the disulfide ligand. They possess principle features already known from the [Fe3E(CO)9]- (E = S, Se, Te) series of complexes (see Fig. 9, Section 1.10.5). 

Carbonylation proceeds in the presence of chalcogen compounds without poisoning Pd catalysts. Pd-catalyzed stereo- and regioselective carbonylative double thiolation of 1-octyne with diphenyl disulfide (3) afforded the (Z)-j6-(phenylthio)--unsaturated thioester 4 [2], The thioester 4 can be converted to 3-(phenylthio)-2-alkenal 5 by Pd-catalyzed reduction with HSnBu3 under mild conditions [3]. When propargyl alcohol was subjected to the carbonylation in the presence of either diphenyl diselenide (6) or disulfide 3, 3-phenylselenobutenolide 7 or 3-phenylthiobutenolide was obtained. The transformation involves isomerization of the acylpalladium intermediate 8 to 9 [4]. 

Compounds Containing M-Group 16 Element Bonds.- Reviews which will be of interest to the reader cover the reaction of Group 13 metal alkyls with O2 and the chalcogens,the alkoxides, thiolates and heavier Group 16 derivatives,and liquid clathrates based on anionic and cationic organoaluminiurns or aluminoxanes. 

Thiolate ligands have dominated the complexes of the heavier chalcogen donors and continue to be employed in stabilizing the dimthenium unit. Many of the catalytic applications found for diruthenium compounds over the last decade have involved thiolate-bridged species. 

---