Homogeneous Catalytic Carbonylation of Nitroaromatics. 6. Synthesis and Structure of Two Bis(carbamoyl) Complexes of Ruthenium

Isopropyl-and benzylamine react with (OC-6-32)-dicarbonylbis(methoxycarbonyl)[1,2-bis(diphenylphosphino)-ethane] ruthenium(II), at room temperature by substituting rapidly both of the methoxy groups. The bis(carbamoyl) complex (OC-6-32)-dicarbonylbis(N-isopropylcarbamoyl)[1,2-bis(diphenylphosphino)ethane]ruthenium(II) was fully characterized using solution spectroscopy and single-crystal X-ray diffraction [monoclinic crystal system, P2₁/c space group, a = 9.083(3) Å, b = 22.28(1) Å, c = 19.599(9) Å, β = 98.62(3)°, V= 3921(10) ų, Z = 4], In addition to the analogous product, the reaction with benzylamine also produced a small amount of crystalline product in which a CO ligand was substituted with benzylamine. This was characterized by single-crystal X-ray diffraction methods as (OC-6-33)-benzylaminecarbonylbis(benzylcarbamoyl)[1,2-bis(diphenylphosphino)ethane]ruthenium(II) [monoclinic crystal system, P2₁/n space group, a = 15.777(5) Å, b = 16.87(2) Å, c = 16.39(2) Å, β = 93.97(6)°, V = 4351(10) ų, Z = 4].