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This work describes the carbonylation of hex-1-ene, cyclohexene, 2,3-dimethyl-but-1-ene and 2-methyl-pent-2-ene, their quaternary mixture and a real Venezuelan naphtha, catalyzed by a rhodium(I) [Rh(cod)(4-picoline)2](PF6) (cod = 1,5-cyclooctadiene) complex immobilized on poly(4-vinylpiridine) (P(4-VP)) in contact with methanol under carbon monoxide atmosphere. The conversion (%) of olefins to carbonylated products for the individual olefins decreases in the order: hex-1-ene (63) > cyclohexene (58) > 2,3-dimethyl-but-1-ene (50) > 2-methyl-pent-2-ene (31), under the following conditions: 0.5 g of P(4-VP) for [Rh] = 2 wt.% (1 × 10−4 mol), 10 mL of CH3OH, [olefin] = 1 × 10−2 mol, S/C = 100, P(CO) = 33 atm at 110 °C for 24 h. Other products such as H2 and CO2 coming from the catalysis of the water–gas shift reaction are observed. In this work, the carbonylation of hex-1-ene, cyclohexene, 2,3-dimethyl-but-1-ene and 2-methyl-pent-2-ene, their quaternary mixture and a real Venezuelan naphtha, catalyzed by a rhodium(I) [Rh(cod)(4-picoline)2](PF6) (cod = 1,5-cyclooctadiene) complex immobilized on poly(4-vinylpiridine) (P(4-VP)) in contact with methanol under carbon monoxide atmosphere is described.

The synthesis, characterization, and catalytic properties of the zero-valent, group six metal complex formed by the reaction of [Mo(CO)3(CH3CN)3] and poly(4-vinylpyridine) (P(4-VP)) is described in this work. The pyridyl groups of the organic polymer are covalently bonded to the Mo centers as suggested by X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and Fourier transform infrared (FT-IR) techniques. The polymer-immobilized metal catalyst was also characterized by DTA–TGA, differential scanning calorimetry (DSC) analysis and its morphology and elemental analyses were studied by scanning electron microscopy/energy dispersive X-ray (SEM/EDX) techniques. In the presence of 2-ethoxyethanol the solid is an active catalyst for the heterogeneous hydrogenation of styrene to ethyl benzene.

The hydrodechlorination of chlorobenzene to benzene and biphenyl was studied using poly(4-vinylpyridine)-immobilized Cu catalysts under CO in basic (NaOH, N(C 2 H 5 ) 3 or Na(CH 3 CO 2 )) aqueous 2-ethoxyethanol medium. This Cu system also catalyzed the water gas shift reaction. The catalytic activities for hydrodechlorination of chlorobenzene to benzene were studied as functions of the reaction parameters (nature of the base, reaction time, [Cu], P(CO), T, and S/C). Among the different base studied activity is maximum for NaOH. The rate of benzene formation displays a first-order dependence on [Cu] over the range 1.25 12.50 wt%. This observation was interpreted in terms of the presence of active species having the same nuclearity. The catalytic activity towards benzene formation proved to be first order dependence on P(CO) over the range 5-35 atm. The kinetics behavior with respect to P(CO) leads to the proposal that CO addition to the catalytic species precedes the rate-limiting step. The catalytic activity proved to be non-linear in chlorobenzene/Cu content, over the range 50-400 molar ratio. The results suggest that the rate-limiting step is preceded by reversible oxidative addition of chlorobenzene to Cu immobilized species.

Rhodium(I) complexes of the type, cis-[Rh(CO)2(amine)2](PF6) where (amine = 3-picoline, 2-picoline, pyridine, 2,6-lutidina or 3,5-lutidine) dissolved in 80% aqueous amine solutions catalyzed the selective reduction of 4-nitrobenzoic acid to 4-aminobenzoic acid under CO atmosphere. The importance of these catalytic systems is their high chemo selectivity for the aromatic nitro group of the 4-nitrobenzoic acid with respect to the carboxylic group, allowing the production of the desired aromatic amine in high yields. The 4-aminobenzoic acid production depends on the nature of the coordinated amine. The Rh/3,5-lutidine system, the most active catalyst among tested, displays turnover frequencies for 4-aminobenzoic acid production of about 173 moles per mole Rh per day for [Rh] = 1 × 10−4 mol, [4-nitrobenzoic acid] = 3.82 × 10−3mol, 10 mL of 80% aqueous 3,5-lutidine, P(CO) = 0.9 atm at 100 °C. Analyses of kinetic results for the Rh/3,5-lutidine system show a first order dependence on 4-nitrobenzoic acid concentration, a non-linear dependence on CO pressure, a segmented Arrhenius plot and dependence on the nature of the reducing gas agent. These data are discussed in terms of a possible mechanism.