Oxidative-addition of PhTe(2)Ph to the furyne cluster [Ru(3)(CO)(7)(mu-H)(mu(3)-eta(2)-C(4)H(2)O){mu-P(C(4)H(3)O)(2)}(mu-dppm)] (1) results in the isolation of four complexes; (i) the previously reported 54-electron cluster [Ru(3)(CO)(6)(mu(3)-Te)(2)(mu-TePh)(2)(mu-dppm)] (5) which results from elimination of trifuryl phosphine, (ii) the furenyl cluster [Ru(3)(CO)(5)(mu-eta(2)-C(4)H(3)O){mu-P(C(4)H(3)O)(2)}(mu-TePh)(2)(mu-dppm)] (6) which results from carbon-hydrogen bond formation and (iii) two new 50-electron complexes [Ru(3)(CO)(5)(mu-H)(mu(3)-eta(2)-C(4)H(2)O){mu-P(C(4)H(3)O)(2)}(mu-TePh)(2)(kappa(2)-dppm)] (7) and [Ru(3)(CO)(4)(mu-H){P(C(4)H(3)O)(3)}(mu(3)-eta(2)-C(4)H(2)O){mu-P(C(4)H(3)O)(2)}(mu-TePh)(2)(kappa(2)-dppm)] (8) both containing unsymmetrical furyne ligands. The structures of all the new compounds have been unambiguously established by single crystal X-ray crystallography. Further reactivity studies have provided a clear understanding of the relative sequence of the key oxidative-addition and reductive-elimination processes, showing that 6 is an intermediate in the formation of 7. DFT calculations have been used to shed light on the unsymmetrical binding of the furyne ligand in 7 and also to show that the adopted position of the heteroatom within the furyne ring can vary within complexes of this type. (C) 2010 Elsevier B.V. All rights reserved.