LAUSR

Abstract Halide bridged arene d6 platinum group metal precursors on treatment with thiourea derivatives (L1 and L2) yielded a series of neutral mono-dentate complexes (1–8). In general complexes have been formulated as [(arene)M(L)к1(S)Cl2] where L = L1, M = Ru, arene = p-cymene 1; benzene 2; arene = Cp*, M = Rh 3 and Ir 4; L = L2, M = Ru, p-cymene 5; benzene 6; arene = Cp*, M = Rh 7 and Ir 8. Structural studies revealed that thiourea ligand coordinate to the metal in a mono-dentate fashion via S atom. Further treatment of mono-dentate complexes 1 and 5 with NaN3 in polar solvent resulted in the formation of highly strained к2(N,S) azido complexes 9 and 10 whereas reaction of complex 7 yielded a six membered ring к2(S,O) azido complex 11. Reaction of complex 9 with dimethylacetylene dicarboxylate (DMAD) and diethylacetylene dicarboxylate (DEAD) leads to the formation of nitrogen (N2) bound triazolato complexes 12 and 13 whereas reaction of complex 11 with the same yielded nitrogen (N1) bound triazolato complexes 14 and 15. However reaction of complex 10 with both DMAD and DEAD leads to decomposition of the products. All these complexes have been characterized by various spectroscopic techniques. The molecular structures of the representative complexes 1, 2, 3, 6, 7, 9, 11 and 12 have been determined by single crystal X-ray diffraction study.