An electron-deficient triosmium cluster containing the thianthrene ligand: Synthesis, structure and reactivity of [Os₃(CO)₉(μ3-η2-C₁₂H₇S₂)(μ-H)]

Reaction of [Os₃(CO)₁₀(CH₃CN)₂] with thianthrene at 80 °C leads to the nonacarbonyl dihydride compound [Os₃(CO)₉(μ-3,4-η²-C₁₂H₆S₂)(μ-H)₂] (1) and the 46-electron monohydride compound [Os₃(CO)₉(μ₃-η²-C₁₂H₇S₂)(μ-H)] (2). Compound 2 reacts reversibly with CO to give the CO adduct [Os₃(CO)₁₀(μ-η²-C₁₂H₇S₂)(μ-H)] (3) whereas with PPh₃ it gives the addition product [Os₃(CO)₉)(PPh₃)(μ-η²-C₁₂H₇S₂)(μ-H)] (4) as well as the substitution product 1,2-[Os₃(CO)₁₀ ((PPh₃)₂] (5) Compound 2 represents a unique example of an electron-deficient triosmium cluster in which the thianthrene ring is bound to cluster by coordination of the sulfur lone pair and a three-center-two-electron bond with the C(2) carbon which bridges the same edge of the triangle as the hydride. Electrochemical and DFT studies which elucidate the electronic properties of 2 are reported

Metal sulfur nitrogen bonded complexes of molybdenum and their X-ray crystal structures

The structure and reactivity of [CpMo(CO)3]2 derived from mono and tri-nuclear molybdenum clusters with nitrogen and sulfur donor ligands are going to be discussed in this paper. Here we used 2-mercaptopyrimidine, 2-mercaptothiazoline, 2-mercaptopyridine, 2-methylbenzimidazole, 2-mercapto-benzothiazole and 2-mercaptobenzoxazole as ligands for the syntheses of the compounds. The reaction of [CpMo(CO)3]2 with 2-mercaptopyrimidine and 2-mercaptothiazoline in refluxing m-xylene at 138 °C gave two novel mononuclear compounds [CpMo(C4H3N2S)(CO)2] (1) [CpMo(C3H4NS2)(CO)2] (2) respectively. Treatment of [CpMo(CO)3]2 with 2-mercaptopyridine, 2-methylbenzimidazole, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole produced the trinuclear clusters [Cp3Mo3(µ-C5H4N)(µ-S)(µ3-S)(CO)2] (3), [Cp3Mo3(-C7H4NNH)(µ-Cl)(µ3-Cl)(CO)2.CH2Cl2] (4), [Cp3Mo3(µ-C7H4NS)2(µ3-S)(µ-S)(µ-CO)2] (5a) and [Cp3Mo3(µ-C7H4NO)2(µ3-S)(µ-S)(µ-CO)2] (5b) respectively. All the compounds have been characterized by IR, 1H NMR and mass spectroscopic data. Structure of compounds 1, 2, 3 and 4 was determined by single crystal X-ray diffraction studies