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Titolo:
Synthesis of Rh(I) and Ir(T) metal complexes with the first two chiral dithiolate ligands derived from carbohydrates
Autore:
Pamies, O; Net, G; Ruiz, A; Bo, C; Poblet, JM; Claver, C;
Indirizzi:
Univ Rovira & Virgili, Dept Quim Fis & Inorgan, E-43005 Tarragona, Spain Univ Rovira & Virgili Tarragona Spain E-43005 , E-43005 Tarragona, Spain
Titolo Testata:
JOURNAL OF ORGANOMETALLIC CHEMISTRY
fascicolo: 2, volume: 586, anno: 1999,
pagine: 125 - 137
SICI:
0022-328X(19990905)586:2<125:SORAIM>2.0.ZU;2-Z
Fonte:
ISI
Lingua:
ENG
Soggetto:
AMINO-ACID PRECURSORS; MOLECULAR-DYNAMICS SIMULATIONS; X-RAY STRUCTURE; ASYMMETRIC HYDROGENATION; RHODIUM COMPLEXES; CATALYST PRECURSORS; SELECTIVE HYDROFORMYLATION; CATIONIC COMPLEXES; FORCE-FIELD; PHOSPHINITES;
Keywords:
rhodium(I); iridium(I); chiral dithiolates; carbohydrate derivatives; DFT molecular orbital calculations;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
105
Recensione:
Indirizzi per estratti:
Indirizzo: Ruiz, A Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Pl Imperial Tarraco1, E-43005 Tarragona, Spain Univ Rovira & Virgili Pl Imperial Tarraco1 Tarragona Spain E-43005
Citazione:
O. Pamies et al., "Synthesis of Rh(I) and Ir(T) metal complexes with the first two chiral dithiolate ligands derived from carbohydrates", J ORGMET CH, 586(2), 1999, pp. 125-137

Abstract

New chiral dithiol compounds 1,2-O-isopropylidene-3,5-dithiol-alpha-D-ribofuranose RiSSH(2) and 1,2-O-isopropylidene-3,5-dithiol-alpha-D-xylofuranoseXySSH(2) and their chiral dithiolate olefinic Rh(I) and Ir(I) complexes [M-2(mu-RiSS)(cod)(2)] (M = Rh 1, Ir 3) and [M-2(mu-XySS)(cod)(2)] (M = Rh 2,Ir 4) were synthesized and characterized. The Rh(I) complexes reacted withCO to give the corresponding binuclear tetracarbonyls [Rh-2(mu-RiSS)(CO)(4)] (5) and [Rh-2(mu-XySS)(CO)(4)] (6), which reacted with two equivalents of PPh3 to form mixed carbonyl-phosphine complexes [Rh-2(mu-RiSS)(CO)(2)(PPh3)(2)] (7) and [Rh-2(mu-XySS)(CO)(2)(PPh3)(2)] (8). The structures of [Rh-2(mu-RiSS)(CO)(4)] (5) and the two possible conformers of [Rh-2(mu-XySS)(CO)(4)] (6a) and (6b) were optimized and their relative stability determined by theoretical methods based on density functional theory (DFT). An interaction between one Rh atom and the oxygen atom of the ring was found in the most stable conformer of [Rh-2(mu-XySS)(CO)(4)]. The complexes [Rh-2(mu-RiSS)(cod)(2)] (1) and [Rh-2(mu-XySS)(cod)(2)] (2) were used as catalytic precursors in the hydroformylation of styrene. The results suggest that mononuclear rhodium hydride carbonyl species are responsible for the catalytic activity. (C) 1999 Elsevier Science S.A. All rights reserved.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 01/12/20 alle ore 09:47:24