Investigation on the reactivity of tetranuclear Group 7/8 mixed-metal clusters toward triphenylphosphine

Abstract

Reactions of the tetranuclear mixed-metal clusters ReM3(CO)13(µ3-thpymS) (1, M = Os; 2, M = Ru; thpymSH = tetrahydropyrimidine-2-thiol) with PPh3 are examined. At room temperature reaction between 1 and PPh3 in the presence Me3NO leads to the formation of mono-and bis-phosphine substituted clusters ReOs3(CO)12(PPh3)(µ3-thpymS) (3) and ReOs3(CO)11(PPh3)2(µ3-thpymS) (4). Cluster 3 also reacts with PPh3 under similar conditions to give 4. In contrast, a similar reaction between 2 and PPh3 furnishes only the monophosphine substituted clusters ReRu3(CO)12(PPh3)(µ3-thpymS) (3). All the new clusters have been characterized by analytical and spectroscopic data together with single crystal X-ray diffraction for 1, 3 and 5.

Alkyl 2-Benzothiazolyl Sulfide Ligated Dirhenium Complexes: Syntheses, Structure and Computational Study of [Re2(CO)8{μ,η1,η1-(R)SCNSC6H4}] (R = CH3 and C2H5)

“…For example, the reactions of Re2(CO)10 with pyridine-2-thiol [1], thioacetamide [2], thiobenzamide [2], diaryl disulfides [3], pyrimidine-2-thiol [4], 2-mercaptothiazoline [5], 2mercaptobenzimidazole [5], 2-mercapto-1-methylimidazole [5], and 2-mercaptobenzoxazole [6] have been reported. Recent advances in research reveal the isolation of mixed metal [7][8][9] and mixed ligand [10][11][12][13] rhenium complexes of sulfur-containing ligands. These reactions often involve the oxidative cleavage of the rhenium-rhenium bond together with the reductive S─H, N─H or S─S bond scission in the ligands [1][2][3][4][5][6].…”