Heterometallic acetylide cluster Cp*WRez(CO)g(CCPh) (la) reacted with thiophenol in refluxing toluene to afford two acetylene clusters Cp*WRe2(CO)a(p3-SPh)(CH=CPh) (2a) and Cp*WRez(C0)7(p-SPh)(CH=CPh) (3a). Their structures were determined by X-ray diffraction studies. Crystal data of 2a: space group I2Ic; a = 20.017(4) A, b = 11.869(6) A, c = 29.622-( 5 ) A, p = 98.50(2)", 2 = 8, R = 0.039, and R, = 0.032 for 3279 observed reflections with I > 2 41). Crystal data of 3a: space group P21In; a = 10.839(5) A, b = 17.112(4) A, c = 16.581-(7) A, p = 94.16(3)", 2 = 4, R = 0.042, and R, = 0.042 for 3323 observed reflections with I > 2 4 n . The structure of 2a possesses a V-shaped core geometry with a face-bridging thiolate ligand and a phenylacetylene adopting a ~3 -7~ (11) mode, whereas cluster 3a contains a triangular skeleton with a n edge-bridging thiolate fragment and a unique p3-q2(1) phenylacetylene ligand. Heating of 2a afforded 3a via elimination of a CO; the latter process could be partially reversed by addition of a CO atmosphere. Upon switching to vinylacetylide clusters Cp*WRe2(CO)g (CCC=CH(CH2)4) (IC) and Cp*WRe2(CO)g(CCCMe=CHd (Id), only the alkylidyne clusters Cp*WRe2(CO)7(p-SPh)z (CCH=C(CH2)5) (4a) and Cp*WRez(C_OMp-SPh)2(CCH=CMe2) (4b) were obtained. C stals of 4a are triclinic, space group P1; a = 10.149(1) A, b = 12.151(4) A, c = 17.442(2)x7 a = 84.79(2)", p = 76.40(1)", y = 70.39(2)", 2 = 2, R = 0.023, and R, = 0.022 for 4557 reflections with I > 2 40. Clusters 4, exhibiting a n open triangular arrangement, possess two thiolate ligands and a n asymmetric vinylalkylidyne weakly bridging a W-Re edge (p-W-C = 1.858(7) A, p-Re-C = 2.339(6) A). n Transition-metal cluster compounds containing alkyne ligands have recently been the focus of considerable attention1 The ability of alkynes to adopt various coordination modes2 and their promising potential in serving as precursors for organic synthesis have promoted extensive investigation of alkyne cluster^.^ Our discovery of a feasible and high-yield method of prepar-+ National Tsing Hua University. I.; Donovan, R. J.; Ingallina, P.; Clos, N.; Shay, W. R.; Eguchi, M.; Zeng, Q.; Korda, A. J . Cluster Sci. 1992, 3, 423. (c) Rudler, H.; Audouin, M.; Chelain, E.; Denise, B.; Goumont, R.; Massoud, A.; Parlier, A.; Pacreau, A.; Rudler, M. Chem. SOC. Rev. 1991,20, 503. (d) Shore, N.