화학공학소재연구정보센터
Inorganic Chemistry, Vol.36, No.1, 64-69, 1997
A Family of Ruthenium Aryls Incorporating an Eta(2)-Bonded Nitrite or Nitrate and a Pendant Imine-Phenol Function
The reaction of carbonylchloro[4-methyl-6-(NR-iminio)phenolato-C-2,O]bis(triphenylphosphine)ruthenium(II), Ru-II(eta(2)-RL)(PPh(3))(2)(CO)Cl (R = Ph, p-MeC(6)H(4)), 1, with NaY (Y = NO2, NO3) has afforded new organometallics of the type carbonyl(nitrito or nitrato)[4-methyl-6-(NR-imino)phenol-C-2]bis(triphenylphosphine)ruthenium(II), Ru-II(eta(1)-RL)(PPh(3))(2)(CO)(eta 2-Y) (2, Y = NO2; 3, Y = NO3). The transformation probably occurs via associative cis attack on chloride by Y-. The reconversion 2 (3) --> 1 is achievable by treating 2 (3) with excess halide. The X-ray structures of Ru(eta(1)-PhL)(PPh(3))(2)(CO)(eta(2)-NO2) and Ru(eta(1)-PhL)(PPh(3))(2)(CO)(eta(2)-NO3) have revealed the presence of (i) O,O’-chelated Y-, (ii) monodentate PhL binding via an aromatic carbon atom lying cis to the CO molecule, and (iii) O(phenolic)... N(imine) hydrogen bonding. The interconversion between 1 and 2 (3) is attended with iminium-phenolate to imine-phenol tautomerization and a change in the rotational conformation of the RL ligand. Crystal data for the complexes are as follows. Ru(eta(1)-PhL)((PPh(3))(2)(CO)(eta(2)-NO2) : crystal system, monoclinic; space group, P2(1)/c; a = 18.597(9) Angstrom, b = 11.947(7) Angstrom, c = 20.362(5) Angstrom, beta = 101.15(3)degrees; V = 4439(4) Angstrom(3); Z = 4; R = 0.0427; R(W) = 0.0458. Ru(eta(1)-PhL)(PPh(3))(2)(CO)(eta(2)-NO3) : crystal system, monoclinic; space group, P2(1)/c; a = 18.726(11) Angstrom, b = 11.857(4) Angstrom, c = 20.443(8) Angstrom, beta = 102.77(4)degrees; V = 4426(3) Angstrom(3); Z = 4; R = 0.0654; R(W) = 0.0659.