@article { ISI:000233432200006, title = {Carbonylation of alkynes, alkenes and alcohols using metal complex catalysts}, journal = {Catalysis Surveys from Asia}, volume = {9}, number = {3}, year = {2005}, month = {SEP}, pages = {193-205}, publisher = {SPRINGER/PLENUM PUBLISHERS}, address = {233 SPRING ST, NEW YORK, NY 10013 USA}, abstract = {

Carbonylation of olefins, alcohols and halides using homogeneous as well as heterogeneous catalysts has been discussed. Highlights of contributions on the activity, selectivity and stability of catalysts for carbonylation reactions are discussed. Kinetics and mechanism including characterization of the intermediate catalytic species has also been reviewed. The performance of anchored Pd complexes on mesoporous supports (MCM-41 and MCM-48), water soluble Pd complexes and supported Pd catalysts in carbonylation of aryl alcohols and olefins has been discussed in the context of catalyst-product separation. Some aspects of kinetic modelling and reaction engineering of these multiphase catalytic reactions have also been reviewed.

}, keywords = {Carbonylation, catalysis, Heterogenization, homogeneous, Palladium}, issn = {1571-1013}, doi = {10.1007/s10563-005-7556-x}, author = {Sarkar, B. R. and Chaudhari, Raghunath V.} } @article { ISI:000240352900023, title = {Ossification: a new approach to immobilize metal complex catalysts - applications to carbonylation and Suzuki coupling reactions}, journal = {Journal of Catalysis}, volume = {242}, number = {1}, year = {2006}, month = {AUG}, pages = {231-238}, publisher = {ACADEMIC PRESS INC ELSEVIER SCIENCE}, type = {Article}, address = {525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USA}, abstract = {

A simple approach for immobilization of transition metal complexes is reported here based on the transformation of the complex into its intrinsically insoluble counterpart, thus generating solid molecular catalysts. This approach that we call {\textquoteleft}{\textquoteleft}ossification{\textquoteright}{\textquoteright} is based on a principle, in which the water-soluble analogues of the metal complexes are precipitated out from aqueous solutions as insoluble ionic ensembles having catalytically active metal-centered coordination environments and robust framework. The approach has been illustrated for I{\textquoteright}d complex catalyzed carbonylation and Suzuki coupling reactions. {\textquoteleft}{\textquoteleft}Ossification{\textquoteright}{\textquoteright} was found to be an economically and environmentally attractive alternative to other exotic immobilization methodologies. (c) 2006 Elsevier Inc. All rights reserved.

}, keywords = {Carbonylation, Heterogeneous catalysts, Immobilization, ossification, Palladium complex, Suzuki coupling}, issn = {0021-9517}, doi = {10.1016/j.jcat.2006.05.032}, author = {Sarkar, Bibhas R. and Chaudhari, Raghunath V.} } @article { ISI:000267625000020, title = {Hydroesterification of 2-vinyl-6-methoxynaphthalene using palladium complexes containing chelating nitrogen ligands}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {307}, number = {1-2}, year = {2009}, month = {JUL}, pages = {134-141}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Hydroesterification of 2-vinyl-6-methoxynaphthalene (VMN) to methyl ester of 6-methoxy naphthyl propionic acid (ester of naproxen) has been investigated using palladium complexes containing the chelating N(boolean AND)O and N(boolean AND)N ligands (pyridine-2-carboxylate, 2-acetylpyridine, 2-pyridine-carboxaldehyde, and bipyridine) as catalysts. Palladium complex containing 2-acetylpyridine as the ligand was found to be superior to other Pd-complexes. Both acid and halide promoters were necessary for high activity and selectivity. As an acid promoter, benzenesulfonic acid was found to be more effective compared to p-toluenesulfonic acid. Formation of ether 2-methoxy-6-(1-methoxyethyl)naphthalene and a polymer of VMN was observed in all the reactions. It was observed that active catalytic species generated during carbonylation reaction was responsible for the polymer formation. The effect of various parameters such as solvents, CO pressure, and alcohols on the catalytic activity as well as the selectivity was investigated. The turnover frequency using the complex Pd(acpy)(PPh(3))(OTs)(2) (acpy = 2-acetylpyridine) catalyst was found to be 42 h(-1), which is the highest for the hydroesterification of VMN. (C) 2009 Elsevier B.V. All rights reserved.

}, keywords = {Carbonylation, Hydroesterification, Naproxen, Palladium complex, Polymer of VMN, Promoters}, issn = {1381-1169}, doi = {10.1016/j.molcata.2009.03.021}, author = {Atla, Shashi B. and Kelkar, Ashutosh A. and Chaudhari, Raghunath V.} } @article { ISI:000286850000004, title = {Oxidative carbonylation of amine using water-soluble palladium catalysts in biphasic media}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {334}, number = {1-2}, year = {2011}, month = {JAN}, pages = {20-28}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Application of water-soluble palladium catalysts for oxidative carbonylation of aniline to N,N{\textquoteright} diphenyl urea (DPU) has been reported. The water-soluble palladium catalysts prepared from sulfonated N-containing ligands were found to be highly stable under reaction conditions and easily recyclable due to insoluble urea product in the reaction medium. This is in contrast to the sulfonated phosphine ligands, which are vulnerable to oxidation under reaction conditions, showing poor activity and stability. Commercially available as well as laboratory synthesized ligands were used for preparing water-soluble palladium catalysts, for oxidative carbonylation of aniline. The best activity was obtained for Pd complex with disodium 2,2{\textquoteright}-bipyridine-4,4{\textquoteright}-disulfonate (Bipy-DS) ligand. Under optimized conditions Pd(BipyDS)Pd(OAc)(2) catalyst gave TOF of similar to 210h(-1) with aniline conversion of similar to 97\% with similar to 91\% selectivity for N.N{\textquoteright}-diphenyl urea. It was found that the catalyst was easily reusable up to five times, with negligible loss in the catalytic activity. The effect of reaction parameters was investigated and a plausible reaction mechanism has been proposed. (C) 2010 Elsevier B.V. All rights reserved.

}, keywords = {Amine, Biphasic catalysis, Carbonylation, Urea, Water-soluble palladium catalyst}, issn = {1381-1169}, doi = {10.1016/j.molcata.2010.10.018}, author = {Didgikar, Mahesh R. and Joshi, Sunil S. and Gupte, Sunil P. and Diwakar, Makarand M. and Deshpande, Raj Madhukar and Chaudhari, Raghunath V.} } @article { ISI:000311350000022, title = {Anchored Pd-complexes in mesoporous supports: synthesis, characterization and catalysis studies for carbonylation reactions}, journal = {Catalysis Today}, volume = {198}, number = {1, SI}, year = {2012}, month = {DEC}, pages = {154-173}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Pd(pyca)(PPh3)(OTs) [pyca = 2-picolinate] complex is efficiently anchored inside different mesoporous matrices, such as MCM-41, MCM-48, SBA-15 using a molecular aminopropyl tether moiety employing different synthesis strategies. Thorough characterization of the materials using powder XRD, multinuclear (C-13, Si-29, P-31) CP-MAS NMR, XPS, SEM, N-2-sorption studies etc. confirmed the successful anchoring of the palladium complex to the walls of the support matrices thus establishing the synthesis protocols unambiguously. The catalysts were found to be highly active and selective for the carbonylation of different aryl olefins and alcohols. Consecutive recycling and successful reuse proved the stability and true heterogeneous nature of all the anchored catalysts, which is a substantial advancement over the existing heterogeneous catalysts for carbonylation. (C) 2012 Elsevier B. V. All rights reserved.

}, keywords = {Anchored catalysts, Carbonylation, Immobilization, mesoporous materials, Palladium complex}, issn = {0920-5861}, doi = {10.1016/j.cattod.2012.04.047}, author = {Sarkar, Bibhas R. and Chaudhari, Raghunath V.} } @article {49135, title = {Activity performance and kinetics for glycerol carbonylation with urea over Zn-Co mixed metal oxide catalyst}, journal = {Canadian Journal of Chemical Engineering }, volume = {101}, year = {2023}, month = {APR}, pages = {2075-2093}, type = {Article}, abstract = {

Efficient carbonylation of glycerol using urea with Zn-Co mixed metal oxide (MMO) catalyst has been achieved. Various methods of catalyst preparation were explored for glycerol carbonate (GC) synthesis. The optimized method of catalyst preparation was found to be co-precipitation (CP) with a Zn:Co ratio of 70:30, achieving 81\% glycerol conversion with 97\% GC selectivity. X-ray diffraction (XRD) studies revealed the formation of ZnO, Co-3 O-4, and spinel ZnCo2O4 phases. Thermal treatment given to the catalyst allows insertion of Zn cations into Co3O4 lattice forming ZnCo2O4 phase which was also evidenced in X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Herein, for the first time, reaction kinetics was studied to propose the rate equation, based on which a plausible reaction pathway is proposed involving two-site adsorption of glycerol (basic site) and urea (acidic site), which undergo carbonylation followed by cyclization into GC. A recycle study and hot filtration test have proven the reusability of the catalyst.

}, keywords = {Carbonylation, cyclic carbonate, Glycerol, kinetics, mixed metal oxide}, issn = {0008-4034}, doi = {10.1002/cjce.24587}, author = {Kondawar, Sharda E. and Kasar, Gaytri B. and Khatua, Angshuman S. and Rode, V, Chandrashekhar} } @article {49331, title = {Iron in organometallic transformations: a sustainable substitute for noble metals}, journal = {ChemCatChem}, volume = {16}, year = {2024}, month = {OCT }, type = {Review}, abstract = {

Transition metal catalysis plays a pivotal role in chemical synthesis. Noble metals often grab significant attention in organometallic catalysis due to their high reactivity. However, the serious issues associated with these metals such as low abundance, toxicity, geopolitical limitations, and volatile prices are driving the scientific community to discover sustainable alternatives. In this context, iron appears to be the first choice as an alternative metal due to its unique properties, including a range of stable oxidation states, Lewis acidity, high abundance in the earth{\textquoteright}s crust, and low toxicity. Over the past two decades, substantial progress has been made in iron catalysis. This overview examines the recent developments in iron-catalyzed industrially relevant transformations such as hydroformylation, olefin isomerization, hydrosilylation, hydrophosphination, carbonylation, Wacker-type oxidation, and plastic depolymerization. As witnessed throughout this review, the performance of iron can be significantly altered by suitable ligand selection and by tailoring the electronic and steric properties of the iron center. While noble metals remain the industry work-horse, iron is inching closer and with extensive scientific understanding, it may replace noble metals in the near future. Late transition metals catalyze several reactions and have been the industry work-horse for decades. While, earth abundant metals are rarely used in industrially relevant transformations. In this overview, we examine the recent development in iron-catalyzed industrially relevant reactions such as hydroformylation, olefin isomerization, hydrosilylation, hydrophosphination, carbonylation, Wacker-type oxidation, and plastic depolymerization. Iron is inching closer and may replace noble metals in near future. image

}, keywords = {Alkene Isomerization, alkyne, Carbonylation, depolymerization, Hydrophosphination, Hydrosilylation, iron catalysis}, issn = {1867-3880}, doi = {10.1002/cctc.202400756}, author = {Kumar, Rohit and Tewari, Tanuja and Chikkali, Samir H.} } @article {49418, title = {Kinetic investigation on palladium-catalyzed carbonylation of allyl alcohol}, journal = {International Journal of Chemical Kinetics}, year = {2024}, month = {OCT}, type = {Article; Early Access}, abstract = {

Palladium-catalyzed carbonylation of allyl alcohol to 3-butenoic acid has been investigated. A significant effect of halide promoters, p-tolylsulfonic acid (TsOH), water, solvents, and PPh3 concentration activity and selectivity has been studied. Detailed kinetics of this reaction was investigated in a temperature range of 363-383 K. The influence of parameters such as stirring speed, allyl alcohol, catalyst, benzyltriethylammonium chloride (BTEAC), TsOH concentrations, and CO partial pressures on the activity and selectivity has been studied. An empirical rate equation was suggested and found to be fairly consistent with observed rate data. In addition, the activation energy and kinetic parameters were evaluated.

}, keywords = {allyl alcohol, Carbonylation, halide promoters, kinetics, Mechanism, Palladium}, issn = {0538-8066}, doi = {10.1002/kin.21767}, author = {Tonde, Sunil S. and Rajurkar, Kalpendra B. and Pagar, Nitin S.} }