Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.21/4952
Título: New RuII(arene) complexes with halogen-substituted bis- and tris(pyrazol-1-YL)borate ligands
Autor: Orbisaglia, Serena
Di Nicola, Corrado
Marchetti, Fabio
Pettinari, Riccardo
Martins, Luísa Margarida D. R. S.
Alegria, Elisabete Clara Bastos do Amaral
Silva, Maria de Fátima C. Guedes da
Rocha, Bruno G. M.
Kuznetsov, Maxim L.
Pombeiro, Armando J. L.
Skelton, Brian W.
Sobolev, Alexandre N.
White, Allan H.
Palavras-chave: Arenes
Density functional calculations
Data: Mar-2014
Editora: Wiley-V C H Verlag GMBH
Citação: ORBISAGLIA, Serena; [et al] – New RuII(Arene) Complexes with Halogen-Substituted Bis- and Tris(Pyrazol-1-YL)Borate ligands. Chemistry-A European Journal. ISSN: 0947-6539. Vol. 20, nr. 13 (2104), pp. 3689-3704
Resumo: [RuCl(arene)(-Cl)](2) dimers were treated in a 1:2 molar ratio with sodium or thallium salts of bis- and tris(pyrazolyl)borate ligands [Na(BpBr3)], [Tl(TpBr3)], and [Tl(Tp(iPr,4Br))]. Mononuclear neutral complexes [RuCl(arene)((2)-BpBr3)] (1: arene=p-cymene (cym); 2: arene=hexamethylbenzene (hmb); 3: arene=benzene (bz)), [RuCl(arene)((2)-TpBr3)] (4: arene=cym; 6: arene=bz), and [RuCl(arene)((2)-Tp(iPr,4Br))] (7: arene=cym, 8: arene=hmb, 9: arene=bz) have been always obtained with the exception of the ionic [Ru-2(hmb)(2)(-Cl)(3)][TpBr3] (5), which formed independently of the ratio of reactants and reaction conditions employed. The ionic [Ru(CH3OH)(cym)((2)-BpBr3)][X] (10: X=PF6, 12: X=O3SCF3) and the neutral [Ru(O2CCF3)(cym)((2)-BpBr3)] (11) have been obtained by a metathesis reaction with corresponding silver salts. All complexes 1-12 have been characterized by analytical and spectroscopic data (IR, ESI-MS, H-1 and (CNMR)-C-13 spectroscopy). The structures of the thallium and calcium derivatives of ligand TpBr3, [Tl(TpBr3)] and [Ca(dmso)(6)][TpBr3](2)2DMSO, of the complexes 1, 4, 5, 6, 11, and of the decomposition product [RuCl(cym)(Hpz(iPr,4Br))(2)][Cl] (7) have been confirmed by using single-crystal X-ray diffraction. Electrochemical studies showed that 1-9 and 11 undergo a single-electron (RuRuIII)-Ru-II oxidation at a potential, measured by cyclic voltammetry, which allows comparison of the electron-donor characters of the bis- and tris(pyrazol-1-yl)borate and arene ligands, and to estimate, for the first time, the values of the Lever E-L ligand parameter for BpBr3, TpBr3, and Tp(iPr,4Br). Theoretical calculations at the DFT level indicated that both oxidation and reduction of the Ru complexes under study are mostly metal-centered with some involvement of the chloride ligand in the former case, and also demonstrated that the experimental isolation of the (3)-binuclear complex 5 (instead of the mononuclear 5) is accounted for by the low thermodynamic stability of the latter species due to steric reasons.
Peer review: yes
URI: http://hdl.handle.net/10400.21/4952
DOI: 10.1002/chem.201304406
ISSN: 0947-6539
Aparece nas colecções:ISEL - Eng. Quim. Biol. - Artigos

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