ChemInform Abstract: MECHANISM OF THE CARBONYLATION OF ALCOHOLS AND UNSATURATED COMPOUNDS IN SOLUTIONS OF PALLADIUM(II) COMPLEXES

Computer-Aided Mechanism Elucidation of Acetylene Hydrocarboxylation to Acrylic Acid Based on a Novel Union of Empirical and Formal Methods

“…A mechanism of this type was reported for the first time by Kaliya et al. and further supported by Heck and Zhir-Lebed' et al Convincing evidence for the participation of an M−COOR intermediate was found only for acetylene in the hydrocarbalkoxylation reactions. Correspondingly, the mechanisms involving M−COOR as a key intermediate were called alcoholate .…”

“…An interesting result of the computer-aided generation of mechanistic hypotheses is the conjecture of Pd(COOH) 2 as an intermediate of acrylic acid synthesis (pathways 〈6〉, 〈12〉, 〈13〉, 〈15〉, 〈17〉, and 〈22〉). The formation of this kind of species was considered in the synthesis of oxalates by oxidative carbonylation of alcohols in the presence of palladium(II) complexes …”

“…The formation of this kind of species was considered in the synthesis of oxalates by oxidative carbonylation of alcohols in the presence of palladium(II) complexes. 27 However, the possibility of acetylene insertion into a Pd-COOH bond was not even discussed.…”

Palladium carbonyl complexes

“…When a primary or secondary amine is replaced by a tertiary amine, a methoxycarbonyl derivative of divalent palladium, (PPh 3 )PdCl(COOMe), is formed. 38 This complex has also been synthesised by Zhir-Lebed' et al 39 The formation of complex 1 has been noted in the carbonylation of [(Z 3 -allyl)PdCl] 2 in the presence of PPh 3 in solution in methanol or ethanol (P CO = 4 atm; 293 K). 40 The divalent palladium acetate complex (PPh 3 ) 2 Pd(OAc) 2 is not reduced by carbon monoxide in methanol under mild conditions.…”

Synthesis of Dimethyl Carbonate from Methanol, Carbon Monoxide, and Oxygen Catalyzed by Copper Compounds

“…The carbomethoxide species would be generated by the insertion of coordinated carbon monoxide in the binuclear complex. The formation of copper carbomethoxide species has recently been hypothesized in the reaction between cupric chloride and mercury carbomethoxy acetate to give alkylcarbonates (Zhir-Lebed et al, 1975).…”