Low-temperature N-O bond cleavage in nitrosyl ligands induced by the unsaturated dimolybdenum anion [Mo2(eta(5)-C5H5)2(mu-PPh2)(mu-CO)2]-.
The unsaturated anion [Mo(2)Cp(2)(mu-PPh(2))(mu-CO)(2)](-) (1) (Na(+) salt) reacts with the nitrosyl complexes [MCp'(CO)(2)(NO)]BF(4) (M = Mn, Re; Cp' = eta(5)-C(5)H(4)Me) rapidly at about 193 K. Upon warming of the resulting mixtures up to 243 K orange solutions are obtained, shown to contain the corresponding oxo- and nitride-bridged tetracarbonyl complexes [Mo(2)MCp(2)Cp'(mu-N)(mu-O)(mu-PPh(2))(CO)(4)] as the major product, which could be isolated only for M = Re. Above 253 K, however, these compounds experience spontaneous decarbonylation to yield the unsaturated tricarbonyl derivatives [Mo(2)MCp(2)Cp'(mu-N)(mu-O)(mu-PPh(2))(CO)(3)] (Mo-Mo = 2.840 A for the Mn compound, according to density functional theory (DFT) calculations). These complexes in turn react rapidly with air to give the corresponding dioxodicarbonyl derivatives [Mo(2)MCp(2)Cp'(mu-N)(mu-O)(mu-PPh(2))(O)(CO)(2)] almost quantitatively. The structure of the latter product (M = Re) was determined by X-ray diffraction methods (Mo-Mo = 2.763(1) A). In contrast with the N-O bond cleavage easily taking place in the above reactions, the direct nitrosylation of 1 with N-methyl-N-nitroso-p-toluenesulfonamide induces no bond cleavage process in the nitrosyl ligand, but just gives the electron-precise tricarbonyl derivative [Mo(2)Cp(2)(mu-PPh(2))(CO)(3)(NO)] or, in the presence of CN(t)Bu, a mixture of the new isocyanide complexes [Mo(2)Cp(2)(mu-PPh(2))(CN(t)Bu)(CO)(2)(NO)] and [Mo(2)Cp(2)(mu-PPh(2))(mu-eta(1):eta(2)-CN(t)Bu)(CO)(NO)]. Separate experiments indicated that these isocyanide complexes cannot be converted one into each other, nor can they be obtained through thermal substitution reactions on the above tricarbonyl product.
García
M Esther
ME
Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain.
García-Vivó
Daniel
D
Melón
Sonia
S
Ruiz
Miguel A
MA
Graiff
Claudia
C
Tiripicchio
Antonio
A
D000838:Anions / Q000737:chemistry*; D003080:Cold Temperature; D004563:Electrochemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D008024:Ligands; D008956:Models, Chemical; D008958:Models, Molecular; D009586:Nitrogen Fixation; D010100:Oxygen / Q000737:chemistry*; D013449:Sulfonamides / Q000737:chemistry*
D000838:Anions; D008024:Ligands; D013449:Sulfonamides; D006861:Hydrogen Peroxide; C418734:N-methyl-N-nitrosotoluene-p-sulfonamide; D010100:Oxygen