Coordination and cluster compounds of ruthenium with the [hypho-1,2-S2B6H9](-) ligandt

The reaction between [tmndH][hypho-1,2-S2B6H9] (tmnd = N,N,N',N'-tetramethylnaphthalene-1,8-diamine) and [RuCl(PPh3)(2)(eta(5)-CP)] in CH2Cl2 at room temperature afforded two ruthenathiaboranes, [5-(eta(5)-Cp)-5-(PPh3)-5,4,6-RuCl(PPh3)(2)(eta(5)-Cp)] 1, and [Ru(eta(1)-1,2-S2B6H9)(PPh3)(2)(eta(5)-Cp)], 2, in 6 and 48% yields, respectively. The heating of a solution of [Ru(eta(5)-1,2-S2B6H9)(PPh3)(2)(eta(5)-Cp)] 2 in CH2Cl2 at reflux temperature afforded 1 in 59% yield. Compound 1 could be described as either a hypho nine-vertex {RuS2B6} cluster or a coordination compound of ruthenium which contains a bidentate eta(2)-dithiaborate cluster ligand; the latter description is preferred. Compound 2 contains an eight-atom hypho-type {1,2-S2B6} cage bonded to the ruthenium atom of the {Ru(PPh3)(2)(eta(2)-Cp)} unit by one sulfur atom and may be described as a compound of ruthenium coordinated eta(1)- to the dithiaborate cluster ligand. The reaction between [tmndH][hypho-1,2-S2B6H9] and [RuCl2(eta(5)-MeC6H4Pri)](2) in CH2Cl2 at room temperature afforded [5-(eta(6)-MeC6H4Pri)-arachno-5,4,6-RuS2B6H8], 3, in 94% yield. Further reaction of 3 and PMePh2 afforded another arachno {RhS2B6}cluster, [5-(eta(6) -MeC6H4Pri)-8-(PMePh2)-arachno-5,4,6-RuS2B6H6], 4, in 25% yield. Compounds 1, 2 and 4 were characterised with single crystal X-ray analyses.