Synthesis and characterization of the cluster compounds containing double C2M2 (M=Co, Mo) cores.: The single-crystal X-ray structures of [O(CH2C2H-μ)2][Co2(CO)6]2 and [O(CH2C2H-μ)2][Mo2(C5H5)2(CO)4]2

The treatment of dipropargyl ether with Co-2(CO)(8) in hexane at room temperature gave a new cluster [O(CH2C2H)-mu)(2)][Co-2(CO)(6)](2) 1, which reacts with the cyclopentadienyl tricarbonyl molybdenum anion [Mo(C5H5)(CO)(3)](-) to form the hetero-tetranuclear clusters [O(CH2C2H-mu)(2)][Co-2(CO)(6)][CoMo(C5H5)(CO)(5)] 2 and [O(CH2C2H-mu)(2)][CoMo(C5H5)(CO)(5)](2) 3, respectively. The reaction of Mo-2(C5H4R)(2)(CO)(4) (R=H, COOCH2CH3) with dipropargyl ether gave the homo-dinuclear clusters [HC2CH2OCH2C2H-mu][Mo-2(C5H4R)(2)(CO)(4)] (R=H 4, COOCH2CH3 5) and homo-tetranuclear clusters [O(CH2C2H-mu)(2)][Mo-2(C5H4R)(2)(CO)(4)](2) (R=H 6, COOCH2CH3 7), respectively. The clusters 4 and 5 reacted with Co-2(CO)(8) to produce the novel tetranuclear clusters [O(CH2C2H-mu)(2)][Co-2(CO)(6)][Mo-2(C5H4R)(2)(CO)(4)] (R=H 8, COOCH2CH3 9). All clusters were characterized by C/H analyses and IR and H-1-NMR spectroscopy and the crystal structures of 1 and 6 . 1/2(CH2Cl2) were determined. Crystals of cluster 1 are monoclinic with space group P2(1)/c, a = 18.149(2), b = 7.0111(7), c = 20.807(2) Angstrom, beta = 115.318(7)degrees, V = 2403.7(5) Angstrom(3), Z = 4 and R = 0.030, R-w = 0.031. Crystals of cluster 6 . 1/2CH(2)Cl(2) are triclinic with space group P (1) over bar, a = 7.92(3), b = 13.360(3), c = 17.208(4) Angstrom, alpha = 109.15(1), beta = 92.07(2), gamma = 93.34(2)degrees, V = 1714.3(9) Angstrom(3), Z = 2 and R = 0.040, R-w = 0.049. (C) 1999 Elsevier Science S.A. All rights reserved.