1361942-83-7Relevant academic research and scientific papers
Reactivity of triruthenium furyne and thiophyne clusters: Multiple additions of thiolato and selenolato ligands through oxidative addition of S-H and SE-H bonds
Hossain, Md. Iqbal,Sikder, Md. Delwar H.,Ghosh, Shishir,Kabir, Shariff E.,Hogarth, Graeme,Salassa, Luca
, p. 2546 - 2558 (2012)
Reactions of 50-electron furyne and thiophyne clusters Ru 3(CO)7(μ-H)(μ3-η2-C 4H2E){μ-P(C4H3E) 2}(μ-dppm) (1, 2; E = O, S) with thiols, dithiols, and benzeneselenol leads to the oxidative addition of the E-H bonds followed by concomitant elimination of the alkyne (probably as the alkene) to afford a range of new thiolato and selenolato triruthenium complexes. Addition of PhSH or iPrSH in boiling benzene affords the 48-electron clusters Ru 3(CO)5(μ-SR)2{μ-P(C4H 3E)2}(μ-dppm)(μ-H) (3-6; E = O, S; R = Ph, iPr) resulting from the addition of 2 equiv of thiol. In contrast, analogous reactions with 1,2-ethanedithiol and 1,3-propanedithiol yield the 50-electron clusters Ru3(CO)3{μ-S(CH2) nS)2{μ-P(C4H3E) 2}(μ-dppm)(μ-H) (7-10; E = O, S; n = 2, 3), in which four S-H bonds have been activated. A similar multiple addition reaction is seen upon addition of PhSeH to 1, affording the tetraselenolato complexes Ru 3(CO)4(κ1-SePh)(μ-SePh) 3{μ-P(C4H3O)2}(μ-dppm)(μ-H) (11) and Ru3(CO)3(μ-SePh)4{μ-P(C 4H3O)2}(μ-dppm)(μ-H) (12). Reaction of 2 with PhSeH gave the tetraselenolato complex Ru3(CO) 4(κ1-SePh)(μ-SePh)3{μ-P(C 4H3S)2}(μ-dppm)(μ-H) (13) together with bis(seleno)-capped Ru3(CO)5{PPh(C4H 3S)2}(μ3-Se)2(μ-SePh) 2(μ-dppm) (14) resulting from further cleavage of two selenium-carbon bonds and formation of a new carbon-phosphorus bond. The new clusters have been characterized by a combination of analytical and spectroscopic methods, and the molecular structures of 3, 4, 7, 8, and 11 have been determined by single-crystal X-ray diffraction studies. Complexes 7-10 are examples of 50-electron clusters containing three apparent metal-metal bonds; however, DFT calculations carried out for 7 show that the longest metal-metal interaction of 3.119 A is actually held in place by the bridging thiolato and diphosphine ligands and does not represent a direct metal-metal bonding interaction.
