Mixed-metal cluster synthesis: [Re(CO)(3)(mu-S2NC7H4)](2) as a precursor for tri- and tetranuclear 2-mercaptobenzothiolato capped clusters

作者：Ghosh Shishir; Khanam Kamrun N; Hossain Md Kamal; Hossain G M Golzar; Haworth Daniel T; Lindeman Sergey V; Hogarth Graeme; Kabir Shariff E^*

来源：Journal of Organometallic Chemistry, 2010, 695(8): 1146-1154.

DOI：10.1016/j.jorganchem.2010.01.021

• Mixed-metal cluster
• Carbonyls
• 2-Mercaptobenzothiazole
• X-ray structures

The readily prepared [Re-2(CO)(6)(mu-S2NC7H4)(2)] (1) reacts with Group 8 trimetallic carbonyl clusters to yield new mixed-metal tri- and tetranuclear clusters. With [Os-3(CO)(10)(NCMe)(2)] at 80 degrees C the tetranuclear mixed-metal cluster [Os3Re(CO)(13)(mu(3)-C7H4NS2)] (2) is the only isolated product. With Ru-3(CO)(12) products are dependent upon the reaction temperature. At 80 degrees C, a mixture of tetranuclear mixed-metal [Ru3Re(CO)(13)(mu(3)-C7H4NS2)] (5) and the triruthenium complex [Ru-3(CO)(9)(mu-H)(mu(3)-C7H4NS2)] (4) results, while at 110 degrees C a second tetranuclear mixed-metal cluster, [Re2Ru2(CO)(12)(mu(4)-S)(mu-C7H4NS)(mu-C7H4NS2)] (3), resulting from carbon-sulfur bond scission, is the major product. Reaction of 1 With Fe-3(CO)(12) at 80 degrees C furnishes the trinuclear mixed-metal cluster [Fe2Re(CO)(8)(mu-CO)(2)(mu(3)-C7H4NS2)] (6). The reactivity of 6 has been probed with the aim of identifying any metal-based selectivity for carbonyl substitution. Addition of PPh3 in presence of Me3NO at 25 degrees C gives both the mono-and bis(phosphine)-substituted derivatives [Os3Re(CO)(12)(PPh3)(mu(3)-C7H4NS2)] (7) and [Os3Re(CO)(11)(PPh3)(2)(mu(3)-C7H4NS2)] (8). In 7 the PPh3 ligand occupies an axial site on wingtip osmium, while in 8 one PPh3 ligand is equatorially coordinated to wingtip osmium and the other is bonded to a hinge osmium. New complexes have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction studies.

• 出版日期2010-4-15