Structural versatility of 5-methyltetrazolato complexes of (eta5-pentamethylcyclopentadienyl)iridium(III) incorporating 2,2'-bipyridine, N,N-dimethyldithiocarbamate, or 2-pyridinethiolate ligands.

Several new mono- and dinuclear eta (5)-pentamethylcyclopentadienyl (Cp*) iridium(III) complexes bearing 5-methyltetrazolate (MeCN 4 (-)) have been synthesized and their molecular and crystal structures have been determined. For complexes incorporating 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen), both mononuclear kappa N (2)-coordinated and dinuclear mu-kappa N (1):kappa N (3)-bridging MeCN 4 complexes were obtained: [CpIr(bpy or phen)(MeCN 4-kappa N (2))]PF 6 ( 1 or 3) and [{Cp*Ir(bpy or phen)} 2(mu-MeCN 4-kappa N (1):kappa N (3))](PF 6) 3 ( 2 or 4), respectively. It was confirmed by X-ray analysis that the dinuclear complex in 2 has a characteristic structure with a pyramidal pocket constructed from a mu-kappa N (1):kappa N (3)-bridging MeCN 4 (-) and two bpy ligands. In the case of analogous complexes with N, N-dimethyldithiocarbamate (Me 2dtc (-)), yellow platelet crystals of mononuclear kappa N (1)-coordinated complex, [CpIr(Me 2dtc)(MeCN 4-kappa N (1))].HN 4CMe ( 5.HN 4CMe), and yellow prismatic crystals of dinuclear mu-kappa N (1):kappa N (4)-bridging one, [{CpIr(Me 2dtc)} 2(mu-MeCN 4-kappa N (1):kappa N (4))]PF 6 ( 6), were deposited. The kappa N (1)- and kappa N (1):kappa N (4)-bonding modes of MeCN 4 (-) in these complexes presumably arise from the compactness of the Me 2dtc (-) coligand. 6 is the first example in which tetrazolates act as a mu-kappa N (1):kappa N (4)-bridging ligand. Furthermore, the molecular and crystal structures of dinuclear complexes having mu-kappa (2) S, N:kappa S-bridging 2-pyridinethiolate (2-Spy (-)) or 8-quinolinethiolate (8-Sqn (-)) ligands have been determined: [(CpIr) 2(mu-2-Spy or 8-Sqn-kappa (2) S, N:kappa S) 2] ( 7 or 8). These thiolato-bridging complexes were stable toward the addition of 5-methyltetrazole (HN 4CMe), owing to the characteristic intramolecular stacking interaction between the pyridine or the quinoline rings. The 2-Spy complex of 7, however, reacted with an excess amount of Na(N 4CMe), resulting in cleavage of the IrN(py) bond and coordination of MeCN 4 (-) in the mu-kappa N (2):kappa N (3)-bridging mode: [(CpIr) 2(mu-2-Spy-kappa S:kappa S) 2(mu-MeCN 4-kappa N (2):kappa N (3))]PF 6 ( 9). This bridging mode of MeCN 4 (-) was also observed in the triply bridging MeCN 4 complex: [(CpIr) 2(mu-MeCN 4-kappa N (2):kappa N (3)) 3]PF 6 ( 10). In these various MeCN 4 complexes, the structural parameters of the MeCN 4 moiety were not perturbed by the difference in the bonding modes.