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  • Title: Cu(I) dinuclear complexes with tripodal ligands vs monodentate donors: triphenylphosphine, thiourea, and pyridine. A 1H NMR titration study.
    Author: Gennari M, Lanfranchi M, Marchiò L, Pellinghelli MA, Tegoni M, Cammi R.
    Journal: Inorg Chem; 2006 Apr 17; 45(8):3456-66. PubMed ID: 16602807.
    Abstract:
    Complexes [PPh3Cu(Tr(Mes,Me))] (1), [PPh3Cu(Tr(Me,o-Py))] (2), and [PPh3Cu(Br(Mes)pz(o-Py))] (3) (Tr(Mes,Me) = hydrotris[1,4-dihydro-3-methyl-4-mesityl-5-thioxo-1,2,4-triazolyl]borate; Tr(Me,o-Py) = hydrotris[1,4-dihydro-4-methyl-3-(2-pyridyl)-5-thioxo-1,2,4-triazolyl]borate; Br(Mes)pz(o-Py) = hydro[bis(thioxotriazolyl)-3-(2-pyridyl)pyrazolyl]borate; PPh3 = triphenylphosphine) were synthesized by the reaction of dinuclear complexes [Cu(Tr(Mes,Me))]2, [Cu(Tr(Me,o-Py))]2, [Cu(Br(Mes)pz(o-Py))]2, and PPh3. 1-3 were characterized by 1H, 13C, and 31P NMR spectroscopy and ESI-mass spectrometry. Crystal structure analyses were performed for 1 and 2. Both complexes crystallize in the triclinic P space group with the metal in a slightly distorted tetrahedral geometry (S3P coordination) bound by a kappa3-S3 ligand and a PPh3 molecule. The solution molecular structures were investigated by means of variable-temperature (210-310 K, CDCl3, 1-2; 200-310 K, CD2Cl2, 3) and NOESY NMR spectroscopy. The solution structures of 1-2 are in accordance with the X-ray structures, and the complexes do not exhibit fluxional behavior. On the other hand, 3 is subject to an equilibrium between two species with a coalescing temperature of approximately 260 K. DFT geometry optimizations suggest that the major species of 3 consists of the Br(Mes)pz(o-Py) ligand bound to Cu(I) in the kappa3-S2H fashion with two C=S groups and a [Cu...H-B] interaction. A PPh3 completes the copper coordination (S2HP coordination). The complex [TuCu(Tr(Mes,Me))] (4) (Tu = thiourea) was crystallized using an excess of Tu with respect to [Cu(Tr(Me,2-Py))]2 (approximately a 6:1 ratio). The metal adopts a distorted tetrahedral geometry with an overall S3H coordination determined by the bound kappa3-S2H ligand (two C=S groups and a [B-H...Cu] interaction) and by a Tu. The reactivity of dinuclear complexes [Cu(Tr(Mes,Me))]2, [Cu(Tr(Me,o-Py))]2, and [Cu(Br(Mes)pz(o-Py))]2 with monodentate ligands was investigated by means of NMR titrations with PPh3, Tu. and pyridine (Py), and formation constants for the adducts [DCu(L)] (D = monodentate donor, L = tripodal ligand) were determined.
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