Platinum/tin catalyzed hydroformylation of naturally occurring monoterpenes

Gusevskaya, Elena V.; Santos, Eduardo N. dos; Augusti, Rodinei; Dias, Adelson de O.; Foca, Claudia M.

doi:10.1016/s1381-1169(99)00264-2

Cited by 52 publications

(12 citation statements)

References 34 publications

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“…We have been studying the diastereoselective hydroformylation of monoterpenes as a way of better understanding the diastereoselectivity control in hydroformylation employing rhodium complexes [21] or platinum/tin systems [22,23] as catalysts. In a previous work [21] we described the rhodium-catalysed hydroformylation of b-pinene and camphene in the presence of various phosphines and phosphites ancillaries.…”

Section: Introductionmentioning

confidence: 99%

Cationic rhodium(I) complexes containing 4,4′-disubstituted 2,2′-bipyridines: A systematic variation on electron density over the metal centre

Ribeiro

Donnici

Santos

2006

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

Cationic rhodium(I) complexes containing 4,4′-disubstituted 2,2′-bipyridines: A systematic variation on electron density over the metal centre

Ribeiro

Donnici

Santos

2006

Journal of Organometallic Chemistry

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“…This reaction can be promoted by rhodium and cobalt carbonyls [8], such as Rh 6 (CO) 16 and Co 2 (CO) 8 , phosphine-modified rhodium catalyst of the type HRh(CO) x (PR 3 ) y [6], and heterobimetallic catalytic system such as Pt-Sn and Pd-Sn [9,10].…”

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confidence: 99%

Insertion and carbonylation reactions of styrene promoted by [HRh(CO)_x‐ (PMe₃)_3−x] (x = 1, 2) compounds: A theoretical investigation

Dias

Rocha

2008

Int J of Quantum Chemistry

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ABSTRACT:In this work we have applied Quantum Mechanical calculations to investigate the first two elementary steps (olefin insertion and carbonylation) in the hydroformylation of styrene, using the model catalysts of the type [HRh(CO) x (PMe 3 ) 3Ϫx ] (x ϭ 1, 2), which are supposed to be the catalytic species that will be present depending on the CO pressure. The migratory styrene insertion reaction and CO insertion reaction into the metal-alkyl bond were investigated at the MP4(SDQ) level using the BP86 optimized geometries. Additionally the Spin Component Scale procedure on the MP2 and MP3 energies (SCS-MP2 and SCS-MP3) was also applied. It is shown that, at normal hydroformylation conditions and normal CO and H 2 pressure, the active catalytic species is preferentially formed in trans arrangement, trans-[HRh-(CO)(PMe 3 ) 2 ], 2b. Because of the greater steric hindrance around the rhodium atom, the electronic effects of the phosphine do not contribute significantly to the stability of the catalyst. The MPn calculations overestimate the stability of the -complexes, in comparison with the BP86 value, as much as 25 kcal/mol, with large fluctuations along the perturbation series. The activation energies predicted by the BP86 method, in comparison with the MPn results, are underestimated about 5 kcal/mol. The reaction and the coordination energies are very sensitive to the theoretical level employed. Our results indicate that the competitive trapping of the styrene by different catalytic species, one leading to the branched and the other leading to the linear species, as was experimentally proposed to explain the selectivity, only seems to hold if we consider the subsequent CO insertion step. This assumption based only on the olefin insertion reaction, as the selectivity determining step, does not apply since the branched product will always preferentially be formed. All methods employed here predict the selectivity in good agreement with the experimental selectivity of 70-95% in favor of the branched product.

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“…The platinum(II) and palladium(II) complexes (3)(4)(5) were prepared following straightforward synthetic routes, by the reaction of the ligands 1 and 2 with either PtCl 2 (cod) or PdCl 2 (cod) in CH 2 Cl 2 (Scheme 1). The complexes are isolated as either white or yellow solids in moderate to good yields and are air stable as solids and in solution.…”

Section: Resultsmentioning

confidence: 99%

“…Pt and Ru catalysts have been studied mainly for academic interest, while Co and Rh have been used industrially for many years [3]. Platinum(II)-catalyzed hydroformylation in the presence of a SnCl 2 cocatalyst has been thoroughly investigated, particularly in asymmetric reactions where high stereoselectivity is prevalent [4]. Specifically, platinum(II) catalysts containing bidentate diphosphine ligands have demonstrated good activities and selectivities toward the linear aldehyde [5,6].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of [MCl2( n Pr-N(Ph2P)2] (M = Pt, Pd) complexes and hydroformylation of 1-octene using [PtCl2(R-N(Ph2P)2)] (R = benzyl, 2-picolyl, n Pr) complexes

Kistamurthy

Otto

Moss

et al. 2010

Transition Met Chem

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The synthesis and characterization of platinum-(II) and palladium(II) complexes of the type [PtX 2 ( n Pr-N-(Ph 2 P) 2 )] (X = Cl, I) and [PdCl 2 (R-N(Ph 2 P) 2 )] {R = n Pr, p-OMe(C 6 H 4 )} containing aminodiphosphine P,P-bidentate ligands is described. Complexes of the type [PtCl 2 (R-N(Ph 2 P) 2 )] (where R = benzyl, 2-picolyl and n Pr) catalyzed the hydroformylation of 1-octene, albeit at low activities and slightly elevated regioselectivities toward the linear aldehyde, when compared with analogous compounds containing small bite angles.

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Platinum/tin catalyzed hydroformylation of naturally occurring monoterpenes

Cited by 52 publications

References 34 publications

Cationic rhodium(I) complexes containing 4,4′-disubstituted 2,2′-bipyridines: A systematic variation on electron density over the metal centre

Cationic rhodium(I) complexes containing 4,4′-disubstituted 2,2′-bipyridines: A systematic variation on electron density over the metal centre

Insertion and carbonylation reactions of styrene promoted by [HRh(CO)_x‐ (PMe₃)_3−x] (x = 1, 2) compounds: A theoretical investigation

Synthesis and characterization of [MCl2( n Pr-N(Ph2P)2] (M = Pt, Pd) complexes and hydroformylation of 1-octene using [PtCl2(R-N(Ph2P)2)] (R = benzyl, 2-picolyl, n Pr) complexes

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Platinum/tin catalyzed hydroformylation of naturally occurring monoterpenes

Cited by 52 publications

References 34 publications

Cationic rhodium(I) complexes containing 4,4′-disubstituted 2,2′-bipyridines: A systematic variation on electron density over the metal centre

Cationic rhodium(I) complexes containing 4,4′-disubstituted 2,2′-bipyridines: A systematic variation on electron density over the metal centre

Insertion and carbonylation reactions of styrene promoted by [HRh(CO)x‐ (PMe3)3−x] (x = 1, 2) compounds: A theoretical investigation

Synthesis and characterization of [MCl2( n Pr-N(Ph2P)2] (M = Pt, Pd) complexes and hydroformylation of 1-octene using [PtCl2(R-N(Ph2P)2)] (R = benzyl, 2-picolyl, n Pr) complexes

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Insertion and carbonylation reactions of styrene promoted by [HRh(CO)_x‐ (PMe₃)_3−x] (x = 1, 2) compounds: A theoretical investigation