Facile modification of 1,3,5-triaza-7-phosphatricyclo[3.3.1.1(3,7)]decane phosphanes coordinated to ruthenium(II).
Hydridotris(pyrazolyl)borate (Tp) ruthenium (II) complexes containing new phosphane ligands are described. The new complexes were obtained by electrophilic attack to a coordinated 1,3,5-triaza-7-phosphatricyclo[3.3.1.1(3,7)]decane (PTA) ligand. Thus, cationic complexes [RuX{kappa(3)(N,N,N)-Tp}(PPh(3))(1-R-PTA)][Y] (X = Cl, R = H (1), CH(2)Ph (4), CH(2)CH=CH(2) (6), CH(2)C[triple bond]CH (8); X = I, R = CH(2)Ph (5), CH(2)CH=CH(2) (7)) and neutral [RuCl{kappa(3)(N,N,N)-Tp}(PPh(3))(1-I(2)-PTA)] (3) have been synthesized and characterized. For complexes [RuI{kappa(3)(N,N,N)-Tp}(PPh(3))(1-R-PTA)][Y] (R = CH(2)Ph, CH(2)CH=CH(2)) an unprecedented formal C-H activation has been observed in alcohols leading to complexes with 1-methyl-4-phenyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1(3,7)]decane, 4-(2-methoxyethyl)-1-methyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1(3,7)]decane and 1-methyl-4-[2-(propan-2-yloxi)ethyl]-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1(3,7)]decane ligands, respectively, and the mechanism explored through deuteriation experiments. The first I(2)-charge transfer compound between I(2) and a nitrogen which belongs to a ligand coordinated to a transition metal, [RuI{kappa(3)(N,N,N)-Tp}(PPh(3))(1-I(2)-PTA)] is described.
García-Fernández
Almudena
A
Departamento de Química Orgánica e Inorgánica, Instituto de Química Organometálica Enrique Moles (Unidad Asociada al C.S.I.C.), Universidad de Oviedo, 33006 Oviedo, Principado de Asturias, Spain.
Díez
Josefina
J
Gamasa
M Pilar
MP
Lastra
Elena
E