Air-Stable Arene Manganese Complexes as Catalysts for the Syngas-Assisted Direct Reductive Amination, Cyanation of Aldehyde, and CO2 Fixation by Epoxide with High Functional Groups Tolerance.

Manganese complexes [(arene)Mn(CO)3]+ were prepared in one step from arenes and Mn(CO)5Br. They were found to be efficient catalysts in the carbonyl cyanation with TMSCN, CO2 fixation by epoxides, and direct reductive amination in the presence of syngas. The amination reaction tolerated various reducible functional groups. The synergy of carbon monoxide and hydrogen in syngas provides high efficiency of the catalytic system. The developed protocols do not require an inert atmosphere, and the catalysts can be handled in air.

Synthesis and reactivity of cyclobutadiene nickel bromide.

NiBr2 reacts with 3-hexyne in the presence of Mg and EtOH to give the cyclobutadiene bromide complex [(C4Et4)NiBr2]2, which serves as a general precursor for various cyclobutadiene nickel compounds. In particular, complexes with 2-electron ligands (C4Et4)Ni(L)Br2 (L = PPh3, P(OMe)3, pyridine), complexes with bidentate ligands [(C4Et4)Ni(L2)Br]PF6 (L2 = bipyridine, phenanthroline), and nickelacarborane (C4Et4)NiC2B9H11 were obtained from [(C4Et4)NiBr2]2 in 70-95% yields. The reactions of [(C4Et4)NiBr2]2 with an excess of strong ligands, such as tBuNC or dppe, led to the displacement of cyclobutadiene. The structures of the five compounds have been established by X-ray diffraction analysis. The previously reported data on cyclobutadiene nickel complexes have been also reviewed.

General Route to Cyclobutadiene Rhodium Complexes.

Cyclobutadiene rhodium complexes bear high potential for applications in organometallic synthesis and catalysis. We have found that the cyclobutadiene complexes with substitutionally labile p-xylene ligands [(C4 R4 )Rh(p-xylene)](+) can be synthesized in one step from the commercially available bis(ethylene) complex [{(C2 H4 )2 RhCl}2 ], p-xylene, and internal alkynes. The replacement of p-xylene by various ligands provides a general access to other [(C4 R4 )Rh] compounds, such as [(C4 R4 )RhCl]x , [(C4 R4 )RhL3 ](+) , [(C4 R4 )Rh(C5 H5 )], and [(C4 R4 )Rh(arene)](+) . Complex [(C4 Et4 )Rh(p-xylene)](+) also catalyzes an unusual cycloisomerization of a 1,11-dien-6-yne into a bicyclic diene.

A new binuclear oxovanadium(V) complex as a catalyst in combination with pyrazinecarboxylic acid (PCA) for efficient alkane oxygenation by H2O2.

A new binuclear oxovanadium(V) complex [{VO(OEt)(EtOH)}2L] (1) where H4L is bis(2-hydroxybenzylidene)terephthalohydrazide has been synthesized and fully characterized. The combination of 1 with pyrazine-2-carboxylic acid (PCA; a cocatalyst) affords a catalytic system for the efficient oxidation of saturated hydrocarbons, RH, with hydrogen peroxide and air in acetonitrile solution at 50 °C to produce alkyl hydroperoxides, ROOH, as the main primary products. Very high turnover numbers (TONs) have been attained in this reaction: for example, after 2220 min, TON = 44,000 and initial TOF (turnover frequency) = 3300 h(-1) per molecule of complex 1. The estimated activation energy of the cyclohexane oxygenation in the presence of 1/PCA is E(a) = 16 ± 2 kcal mol(-1). This value is identical to that obtained for the cyclohexane oxidation with H2O2 catalyzed by the (n-Bu4N)[VO3]/PCA combination (17 ± 2 kcal mol(-1)). The dependences of initial oxidation rates W0 on the initial concentrations of all components of the reaction mixture have been determined. Based on these kinetic data and on the regio- and bond-selectivity parameters measured in the oxidation of linear and branched alkanes a mechanism of the oxidation has been proposed which includes the generation of hydroxyl radicals in the crucial stage.