Syntheses of four new ruthenium(II) complexes of the [RuCl2(P)2(N)2] type using 2-(diphenylphosphino)ethyl methyl ether (P~O) as ether-phosphine and triphenylphosphine (PPh3) as monodentate phosphine ligands in the presence of [3-(2-aminoethyl)aminopropyl]trimethoxysilane as diamine co-ligand are presented for the first time. The reactions were conducted at room temperature and under an inert atmosphere. Due to the presence of the trimethoxysilane group in the backbone of complexes 1 and 2 they were subjected to an immobilization process using the sol-gel technique in the presence of tetraethoxysilane as cross-linker. The structural behavior of the phosphine ligands in the desired complexes during synthesis were monitored by 31P{1H}-NMR. Desired complexes were deduced from elemental analyses, Infrared, FAB-MS and 1H-, 13C- and 31P-NMR spectroscopy, xerogels X1 and X2 were subjected to solid state, 13C-, 29Si- and 31P-NMR spectroscopy, Infrared and EXAF. These complexes served as hydrogenation catalysts in homogenous and heterogeneous phases, and chemoselective hydrogenation of the carbonyl function group in trans-4-phenyl-3-butene-2-al was successfully carried out under mild basic conditions.
The preparation of new [MeC(CH2PPh2)3CuCl] 1 and its derivatives was carried out directly by mixing of CuCl and MeC(CH2PPh2)3 ligand in dry THF, the neutral precursor 1 served to prepare [MeC(CH2PPh2)3Cu(NCCH3)]BF4 2 and [MeC(CH2PPh2)3Cu(PCH2Ph)3]BF4 3. These complexes are characterized on the basis of elemental analysis, IR, EDS, 1H, 13C and 31P{1H}NMR, FAB-MS, TG/DTA and single-crystal X-ray diffraction studies. Complex 1 crystallizes in the Orthorhombic unit cells with the space group Pna2(1). The structural behavior of MeC(CH2PPh2)3 ligand in the formed complexes during the coordination reaction was monitored by 31P{1H}NMR in CDCl3 at room temperature for the first time.