13938-94-8Relevant articles and documents
Sterically demanding, sulfonated, triarylphosphines: Application to palladium-catalyzed cross-coupling, steric and electronic properties, and coordination chemistry
Moore, Lucas R.,Western, Elizabeth C.,Craciun, Raluca,Spruell, Jason M.,Dixon, David A.,O'Halloran, Kevin P.,Shaughnessy, Kevin H.
, p. 576 - 593 (2008)
Tri(2,4-dimethyl-5-sulfonatophenyl)phosphine trisodium (TXPTS ·Na3) and tri(4-methoxy-2-methyl5-sulfonatophenyl)phosphine trisodium (TMAPTS·Na3) both provide more active catalysts for Suzuki and Sonogashira couplings of aryl bromides in aqueous solvents than tri(3-sulfonatophenyl)phosphine trisodium (TPPTS ·Na3). In the Heck coupling, TXPTS ·Na3 provides the most effective catalyst system. Cone angles determined from DFT-optimized structures show that both TXPTS·Na3 (206°) and TMAPTS·Na3 (208°) are significantly larger than TPPTS·Na3 (165°). The identity of the counterion had a significant effect on the calculated cone angles for these ligands. The electronic properties of these ligands determined by the CO stretching frequencies of trans-RhL2(Cl)CO complexes were identical, although calculated electronic parameters suggest subtle differences between these ligands. Similar to TPPTS·Na3, both TXPTS·Na3 and TMAPTS·Na3 react with Pd(OAc)2 in aqueous solvents to give LnPd0 complexes and the corresponding phosphine oxide. The reduction of palladium(II) by TXPTS·Na3 is significantly slower than is seen with TMAPTS·Na3 or TPPTS·Na3 at room temperature. Evidence of palladacycle complexes derived from TXPTS·Na3 and TMAPTS·Na3 by activation of an ortho-methyl substituent was also observed in ligand coordination studies and under catalytic reaction conditions.
Baird, M. C.,Lawson, D. N.,Mague, J. T.,Osborn, J. A.,Wilkinson, G.
, (1966)
Addison, A. W.,Gillard, R. D.,Sheridan, P. S.,Tipping, L. R. H.
, (1974)
Dolcetti, G.,Hoffman, N. W.,Collman, J. P.
, p. 531 - 542 (1972)
Carbonylation reactions of Rh(PPh3)3Cl and Ru(PPh3)3Cl2 in the solid state
Porta, Francesca,Tollari, Stefano,Bianchi, Claudia,Recchia, Sandro
, p. 79 - 83 (1996)
The carbonylation reactions of Rh(PPh3)3Cl (1) and Ru(PPh3)3Cl2 (2) in the solid state with carbon monoxide at atmospheric pressure were studied; the known complexes Rh(PPh3)2(CO
π-Coordination vs ring-opening isomerization of 2-phenyl-1-methylenecyclopropane upon the reaction with RhCl(PPh3)3
Osakada, Kohtaro,Takimoto, Hisami,Yamamoto, Takakazu
, p. 4532 - 4534 (1998)
The reactions of 2-phenyl-1-methylenecyclopropane with RhCl(PPh3)3 for 16 h at 50°C and at 0°C gave RhCl(η4-CH2=CPhCH=CH2)(PPh 3)2 (1) and RhCl-(η2-CH2=CCH2HPh)(PPh3) 2 (2) as respective isolated products. Heating of a benzene solution of 2 at 50°C turned it into 1 in a low yield (3)3 and with 2 at the same temperature afforded 1 (10%) and 2-phenyl-1,3-butadiene (14%).
Brown, Paul R.,Cloke, F. Geoffrey N.,Green, Malcolm L. H.
, p. 869 - 874 (1985)
Chain initiation efficiency in cobalt- and nickel-mediated polypeptide synthesis
Deming, Timothy J.,Curtin, Scott A.
, p. 5710 - 5717 (2000)
In the presence of certain ligands and solvents, nickel- and cobalt- mediated living polymerizations of α-amino acid-N-carboxyanhydrides (NCAs) produce polymers with molecular weights several times greater than predicted by initial molar ratios of monomer to initiator. Such molecular weight inflation could result either from competitive formation of catalytic intermediates of reduced activity or from incomplete formation of a single catalytically active species. Evidence is presented here supporting the latter possibility. Specifically, evidence is given that the concentration of the key amido - amidate metallacyclic active species is reduced in situ by (1) complexation of metal(0) preinitiator by CO liberated upon addition of an NCA monomer to another molecule of preinitiator, (2) incomplete ring contraction of a six-membered amido - alkylmetallacyclic intermediate due to inefficient proton migration, and (3) dimerization of the amido - amidate active species to give catalytically inactive complexes.
SYNTHESES AND 31P NMR STUDIES OF SOME CHLOROCARBONYLRHODIUM(I) COMPLEXES CONTAINING 1,3-DI-t-BUTYL-2,4-DIHALOGENOCYCLODIPHOSPHAZANES (PXNt-Bu)2(X=Cl, F) AND RELATED LIGANDS
Laurent, James C.T.R. Burckett St.,Sinclair, James,Nixon, John F.
, p. 379 - 390 (1984)
Syntheses of the chlorocarbonylrhodium complexes 2(PFNt-Bu)2>, trans-, x, 2 and trans- are described together with the structurally related x,
Rhodium-Complex-Catalyzed Hydroformylation of Olefins with CO2and Hydrosilane
Ren, Xinyi,Zheng, Zhiyao,Zhang, Lei,Wang, Zheng,Xia, Chungu,Ding, Kuiling
supporting information, p. 310 - 313 (2016/12/30)
A rhodium-catalyzed one-pot hydroformylation of olefins with CO2, hydrosilane, and H2has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of poly(methylhydrosiloxane) (PMHS) mediated CO2reduction to CO and a conventional rhodium-catalyzed hydroformylation with CO/H2. The hydrosilylane-mediated reduction of CO2in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.
Mixed anhydride complexes of rhodium(i) and ruthenium(ii)-their synthesis and ligand rearrangements
Coetzee, Jacorien,Eastham, Graham R.,Slawin, Alexandra M. Z.,Cole-Hamilton, David J.
, p. 3479 - 3491 (2014/03/21)
The coordination chemistry and solution behaviour of Rh(i) and Ru(ii) complexes derived from mixed anhydride ligands of carboxylic acids and phosphorus acids were explored. Similar to the free ligand systems, mixed anhydride complexes rearranged in solution via a number of pathways, with the pathway of choice dependent on the mixed anhydride employed, the auxiliary ligands present as well as the nature of the metal centre. Plausible mechanisms for some of the routes of rearrangement and by-product formation are proposed. Where stability allowed, new complexes were fully characterised, including solid state structures for four of the unrearranged mixed anhydride complexes and two of the interesting rearrangement products.
Rhodium-catalyzed cross-coupling reactions of carboxylate and organoboron compounds via chelation-assisted C-C bond activation
Wang, Jingjing,Liu, Bowen,Zhao, Haitao,Wang, Jianhui
, p. 8598 - 8607 (2013/02/23)
A new rhodium-catalyzed decarbonylated coupling reaction of ethyl benzo[h]quinoline-10-carboxylate and organoboron compounds that occurs through chelation-assisted sp2 C-COOEt bond activation was described. In this system CuCl played a very important role, and a five-membered rhodacycle was also involved as a key intermediate. Various functionalities were compatible in the reaction, and the desired products were obtained in good to excellent yields. DFT calculations on the mechanisms of this reaction using a Rh(I) model catalyst have also been carried out.