Reaction of the chlorogermylene ArGeCl [Ar ) 2,6-bis((diethylamino)methyl)phenyl] with lithium amides afforded the aminogermylenes ArGeNR 2 1 (1a, R ) SiMe 3 ; 1b, R ) i Pr); 1a was structurally analyzed by X-ray diffraction. A protic reagent such as 2,4,6-trimethylphenol (Ar′OH) reacts with 1b, leading to the mesityloxygermylene ArGeOAr′ 2. Subsequent hydrolysis of tungsten complexes 1‚W(CO) 5 gave ArGeOH‚W(CO) 5 , 3. From 1a, ArGeOSiMe 3 ‚ W(CO) 5 (4) also was obtained. Compounds 3 and 4 are the first stable hydroxy-and siloxygermylene complexes. X-ray analysis of 3 shows an increased coordination of the sidechain nitrogen atoms to the germanium resulting from the complexation GefW. This complexation can also explain the significant acidity of the hydroxy group in 3, in the same range as triphenylgermanol Ph 3 GeOH.

The reaction of [(Cymene)RuCl2]2 with the chelate LiHC(PPh2NPh)2 occurs to remove both chloride ligands, to furnish a cationic Ru(II) complex with the monoanionic ligand bound eta3, through two N and an sp3 carbon. This cation is also produced from the conjugate acid of the ligand H2C(PPh2NPh)2 because this molecule can serve as a Brønsted base, to deprotonate the acidic carbon of another molecule of H2C(PPh2NPh)2. DFT calculations show an energy surface where (Cymene)RuHC(PPh2NPh)2L is more stable with a Ru-CH(PPh2NPh)2 bond and with L = Cl- or MeCN not coordinated to Ru, than to an eta2-HC(PPh2NPh)2 structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated eta3 vs analogous diketiminates is discussed. The nucleophilicity of Cgamma in structure 1, vs that of donors L = Cl- or MeCN, is evaluated to understand the preference of the bis(phosphinimino)methanide to be bidentate or tridentate.

The preparation of several new molybdenum(VI) complexes containing Schiff base ligands tagged with sulfonate functionalities is presented. The title compounds have been characterized by standard analytical methods including NMR, IR, and mass spectroscopy. Xray structures of the N-salicylidene-2-aminophenolate dioxidomolybdenum complexes bearing sulfonato groups on the salicylidene moiety (as the sodium and ammonium salts) are described herein accompanied by the structural characterization of the N-salicylidene-2aminoethanolate sulfonate Schiff base ligand. The activity of the ionic catalysts for cyclooctene epoxidation is shown in different room temperature ionic liquids (i.e. [BMIM][NTf2] (NTf2 -= (CF3SO2)2N -), [BMIM][CF3SO3], [EMIM][CH3C6H4SO3]).