13938-94-8Relevant academic research and scientific papers
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.
Carbene Complexes. Part 18. Synthetic Routes to Electron-rich Olefin-derived Monocarbenerhodium(I) Neutral and Cationic Complexes and their Chemical and Physical Properties
Doyle, Michael J.,Lappert, Michael F.,Pye, Peter L.,Terreros, Pilar
, p. 2355 - 2364 (1984)
Electron-rich olefins of general type C(NR)CH2CH2NR>2 (LR2; R=Me, Et, Ph, 4-MeC6H4. 4-MeOC6H4, or 2-MeOC6H4) undergo reaction with a variety of rhodium(I) precursors via ligand displacement or chloride-bridge cleavage to afford monocarbenerhodium(I) complexes, such as R)(PPh3)2>, R)>, or R)(PPh3)>>LR= =C(NR)CH2CH2NR, cod=cyclo-octa-1,5-diene>; complexes Me)(PPh3)X> Me= =CN(Me)CH2CH2CH2NMe, X= CO or PPh3> have similarly,been obtained from the olefin L'Me2.From these, further complexes may be obtained by ligand (neutral or anionic) exchange processes : trans-R(PPh3)2>, trans-R)(PPh3)2>X (X=Br, Cl, ClO4, or I), R)(PPh3)> (X=BH4 or ClO4), cis-R)> (X=Cl or NO3), R)> (X= CH2SiMe3, ClO4, or NO3), cis-R)(PPh3)>, and R)>.In many of the reactions some of these ligand displacements at RhI proceed without retention of stereochemistry and it is likely that the observed product is the thermodinamically preferred isomer.Other chemical properties of the monocarbenerhodium(I) complexes relate to (i) rare examples of the displacement of LR from Rh by PPh3 or Ph2PCH2CH2PPh2 under rather forcing conditions, and (ii) oxidative addition (not particularly facile) of HCl, Cl, or C2(CN)4.The 45 new complexes heva been characterised by analysis and spectroscopy (i.r. and 1H and 31P n.m.r.) and, where appropriate, relative molecular mass determination , and electrical conductivity.From J(31P-103Rh) coupling constants it is concluded that LR has a greater trans influence than PPh3 but a lower cis influence.
Photochemical Behavior of Chlorocarbonylbis(triphenylphosphine)rhodium(I), ClRh(CO)P2 (P = PPh3). Laser Flash Photolysis with Infrared Detection
Oishi, Shigero,Kawashima, Takeshi
, p. 747 - 750 (1992)
Laser flash photolysis of ClRh(CO)P2 with monitoring infrared region gave definite evidence of photoelimination of CO, rather than P.ClRhP2 generated reacts with the remaining ClRh(CO)P2 to give a transient binuclear rhodium carbonyl, which regenerates ClRh(CO)P2 via the reaction with CO.
PHOSPHINERHODIUM COMPLEXES AS HOMOGENEOUS CATALYSTS XI. DECARBONYLATION OF PRIMARY ALCOHOLS USED AS SOLVENTS UNDER CONDITIONS OF OLEFIN HYDROGENATION; A SIDE REACTION LEADING TO CATALYST DEACTIVATION
Kollar, Laszlo,Toeroes, Szilard,Heil, Balint,Marko, Laszlo
, p. 253 - 256 (1980)
In the hydrogenation of olefins in alcoholic solvents catalysed by phosphinerhodium complexes a hydrogen transfer reaction from the alcohols to the olefins takes place alongside the main reaction.With primary alcohols the aldehydes formed are decarbonylated and the in situ catalysts formed from 2 and phosphines are partially converted into Rh(CO)(PR3)2Cl type complexes and thereby deactivated.
Remarks on the process of homogeneous carbonylation of rhodium compounds by N,N-dimethylformamide
Varshavsky, Yuri S.,Cherkasova, Tatiana G.
, p. 887 - 893 (2007)
Reductive carbonylation of rhodium(III) chloride complexes, commercial RhCl3 · nH2O neutralized with BaCO3, (Me2NH2)2[RhCl5(DMF)], (PPh4)[RhCl4(H2/sub
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
THE CATALYTIC SUBSTITUTION OF METAL CARBONYL AND SUBSTITUTED METAL CARBONYLS BY ISONITRILES IN THE PRESENCE OF RHODIUM(I) AND POLYMER-SUPPORTED RHODIUM(I) COMPLEXES
Albers, Michel O.,Coville, Neil J.,Nicolaides, Christakis P.,Webber, Ronald A.
, p. 247 - 250 (1981)
Metal carbonyls and substituted metal carbonyls, under relatively mild reaction conditions, in the presence of isonitriles, undergo catalytic CO substitution by rhodium(I) and polymer-supported rhodium(I) complexes.The reaction provides a facile route to te synthesis of transition metal isonitrile complexes.
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%).
Insertion Reactions of the Fragment into a Phosphirene Ring, and Carbonylation of the resulting Rhodium(III) Complex. Crystal and Molecular Structures of Ph(PPh3)2>, O(PPh3)2> and the Novel Dimeric Complex O(PPh3)>2>
Ajulu, Florence A.,Carmichael, Duncan,Hitchcock, Peter B.,Mathey, Francois,Meidine, Mohamed F.,et al.
, p. 750 - 752 (1992)
The first example of insertion of the d8Rh(I) fragment into a phosphirene ring system results in a five-coordinate Rh(III) complex, which undergoes insertion of carbon monoxide to give either monomeric O(PPh3)2> or dimeric O(PPh3)>2>, the structures of which have been elucidated by NMR spectroscopy and single-crystal X-ray diffraction studies.
Peripheral SH-functionalisation of carbosilane dendrimers including the synthesis of the model compound dimethylbis(propanethiol)silane and their interaction with rhodium complexes
Camerano, Jose A.,Casado, Miguel A.,Ciriano, Miguel A.,Tejel, Cristina,Oro, Luis A.
, p. 3092 - 3100 (2005)
Treatment of the allyl-containing compounds Me2Si(CH 2CH=CH2)2 and MeSi(CH2CH=CH 2)3 with thioacetic acid in the presence of AIBN gave Me2Si[(CH2)3SC(O)CH3]2 and MeSi[(CH2)3SC(O)CH3]3, respectively, which were reduced with LiAlH4 to the dithiols Me 2Si[(CH2)3SH]2 (3) and MeSi[(CH 2)3SH]3 (4). This protocol was applied to the first and second generations of the doubly and triply-branched carbosilane allyl dendrimers, Si[(CH2)3SiMe(CH2-CH=CH 2)2]4 (G(1)allyl-8), Si[(CH 2)3SiMe{(CH2)3SiMe(CH 2CH=CH2)2}2]4 (G(2) ally-16), Si[(CH2)3Si(CH2CH=CH 2)3]4 (G(1)allyl-12), and Si[(CH2)3Si{(CH2)3Si(CH 2CH=CH2)3}3]4 (G(2) allyl-36) to give the corresponding SH functionalised surface dendrimers Si[(CH2)3SiMe(CH2CH 2CH2SH)2]4 (G(1)SH-8), G(2)SH-16, G(1)SH-12, and G(2)SH-36. Reactions of 3 with [M(acac)(diolefin)] (M = Rh, Ir; diolefin = 1,5-cyclooctadiene, 2,5-norbornadiene) gave the compounds of the type [M2(μ-Me 2Si[(CH2)3S]2)(diolefin) 2]n. These diolefin complexes are octanuclear (n = 4) in solution while the complex [Rh2(μ-Me2Si[(CH 2)3S]2)(cod)2]n (5) is tetranuclear in the solid state. The structure of 5, solved by X-ray diffraction methods, consists of a 20-membered metallomacrocycle formed by two dimethylbis(propylthiolate)silane moieties bridging four fragments Rh(cod) in a μ2 fashion through the sulfur atoms. Treatment of [Rh(acac)(CO)2] with 3 gave [Rh2(μ-Me 2Si[(CH2)3S]2)(CO)4] n, which is a mixture of tetra (n = 2) and octanuclear (n = 4) complexes in a 2: 1 ratio in solution, while the related complex [Rh 2(μ-Me2Si[(CH2)3S] 2)(CO)2(PPh3)2]2 is tetranuclear. Reactions of [Rh(acac)(L-L)] (L-L = cod, (CO)2, (CO)(PPh3)) with 4 and the dendrimers G(1)SH-8, G(2) SH-16, and G(1)SH-12, gave microcrystalline solids of formulae [Rh3(MeSi[(CH2)3S] 3)(L-L)3]n, [Si[(CH2) 3SiMe{(CH2)3SRh(cod)}2] 4]n ([G(1)Rh(cod)-8]n), [Si[(CH 2)3Si{(CH2)3SRh(cod)} 3]4]n ([G(1)Rh(cod)-12] n), etc., which presumably are tridimensional coordination polymers. The Royal Society of Chemistry 2005.
