Four hexanuclear molybdenum chloride cluster complexes containing terminal thiolate ligands have been synthesized and fully characterized. (Bu 4N) 2[Mo 6Cl 8(SEt) 6] was prepared by reacting Na 2[Mo 6Cl 8(OMe) 6] with an excess of ethanethiol in refluxing tetrahydrofuran. (PPN) 2[Mo 6Cl 8(SBu) 6], (Bu 4N) 2[Mo 6Cl 8(SBn) 6], and (Bu 4N) 2[Mo 6Cl 8(SNC 8H 6) 6] (C 8H 6NS (-) = 3-indolylthiolate) were subsequently prepared in the reaction of [Mo 6Cl 8(SEt) 6] (2-) with an excess of HSR (R = Bu, Bn or 3-indolyl). Single crystal X-ray diffraction analyses were performed on two of these complexes: (PPN) 2[Mo 6Cl 8(SEt) 6].Et 2O, crystallizes in the triclinic space group P1 with a = 12.3894(11), b = 13.7651(12), c = 15.0974(13), alpha = 103.975(2), beta = 99.690(2), gamma = 98.062(2), and Z = 1; (PPh 3Me) 2[Mo 6Cl 8(SBn) 6].2NO 2CH 3, also crystallizes in the P1 space group with a = 12.1574(16), b = 13.4441(17), c = 14.2132(18), alpha = 89.654(2), beta = 88.365(2), gamma = 71.179(2), and Z = 1. Our studies demonstrate that [Mo 6Cl 8(SEt) 6] (2-) displays luminescent properties and that the same complex undergoes substitution reactions with different thiols, as well as reaction with electrophilic reagents such as MeI.

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Sodium in dry methanol reduces 2-cyanopyridine in the presence of 3-piperidylthiosemicarbazide and produces 2-pyridineformamide-3-piperidylthiosemicarbazone, HAmpip. Complexes with zinc(II), cadmium(II), and mercury (II) have been prepared and characterized by elemental analyses and spectroscopic techniques. In addition, the crystal structures of [Zn(Ampip) 2 ], [Zn(Ampip)(Oac)] 2 , [Cd(HAmpip)Cl 2 ]·(CH 3 ) 2 SO, [Cd(HAmpip)Br 2 ] · (CH 3 ) 2 SO, [Cd(HAmpip)I 2 ]·(CH 3 ) 2 SO, [Cd(Ampip) 2 ]and [Hg(HAmpip)Br 2 ]·(CH 3 ) 2 SO have been solved. Coordination of the anionic and neutral thiosemicarbazone ligand is via the pyridyl nitrogen, imine nitrogen and thiolato/thione sulfur atom,