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Titolo:
BASAL SITE SUBSTITUTION IN THE SULFIDE-BRIDGED CLUSTER RU-3(CO)(9)(MU(3)-S)(2) BY THE REDOX-ACTIVE DIPHOSPHINE 4,5-BIS(DIPHENYLPHOSPHINO)-4-CYCLOPENTEN-1,3-DIONE (BPCD) - SYNTHESIS, X-RAY STRUCTURE AND ELECTROCHEMICAL PROPERTIES OF RU-3(CO)(7)(BPCD)(MU-S)(2)
Autore:
SHEN HF; BOTT SG; RICHMOND MG;
Indirizzi:
UNIV N TEXAS,DEPT CHEM,CTR ORGANOMET RES & EDUC DENTON TX 76203 UNIV N TEXAS,DEPT CHEM,CTR ORGANOMET RES & EDUC DENTON TX 76203
Titolo Testata:
Inorganica Chimica Acta
fascicolo: 2, volume: 241, anno: 1996,
pagine: 71 - 79
SICI:
0020-1693(1996)241:2<71:BSSITS>2.0.ZU;2-4
Fonte:
ISI
Lingua:
ENG
Soggetto:
ELECTRON-TRANSFER; LIGAND SUBSTITUTION; 2,3-BIS(DIPHENYLPHOSPHINO)MALEIC ANHYDRIDE; TRIIRON CLUSTERS; TETRAHEDRANE CLUSTER; MOLECULAR-STRUCTURE; CARBONYL-COMPLEXES; CRYSTAL-STRUCTURE; ACTIVATION; DERIVATIVES;
Keywords:
CRYSTAL STRUCTURES; ELECTROCHEMISTRY; RUTHENIUM COMPLEXES; CARBONYL COMPLEXES; SULFIDE-BRIDGED COMPLEXES; CLUSTER COMPLEXES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
57
Recensione:
Indirizzi per estratti:
Citazione:
H.F. Shen et al., "BASAL SITE SUBSTITUTION IN THE SULFIDE-BRIDGED CLUSTER RU-3(CO)(9)(MU(3)-S)(2) BY THE REDOX-ACTIVE DIPHOSPHINE 4,5-BIS(DIPHENYLPHOSPHINO)-4-CYCLOPENTEN-1,3-DIONE (BPCD) - SYNTHESIS, X-RAY STRUCTURE AND ELECTROCHEMICAL PROPERTIES OF RU-3(CO)(7)(BPCD)(MU-S)(2)", Inorganica Chimica Acta, 241(2), 1996, pp. 71-79

Abstract

The sulfide-bridged cluster Ru-3(CO)(9)(mu(3)-S)(2) (1) has been allowed to react with the redox-active diphosphine ligand 4,5-bis(diphenylphosphino) -4-cyclopenten-1,3-dione (bpcd) in the presence of Me(3)NO to give the new cluster Ru-3(CO)(7)(bpcd)(mu(3)-S)(2) (2) in 61% yield. The ancillary bpcd in 2 is bound at one of the basal ruthenium sitesin a chelating fashion, being derived by the replacement of axial andequatorial CO groups. This cluster represents the first example of a cluster derived from Ru-3(CO)(9)(mu(3)-S)(2) that contains a chelatingdiphosphine ligand. Cluster 2 has been characterized in solution by IR and NMR (H-1 and P-31) spectroscopies and in the solid state by X-ray diffraction analysis. Ru-3(CO)(7)(bpcd)(mu(3)-S)(2), which exists astwo crystallographically independent molecules in the unit cell, crystallizes in the monoclinic space group P2(1)/c, a = 19.451(1), b = 21.865(2), c = 20.982(2) Angstrom, beta = 116.011(6)degrees, V = 8019.7(10) Angstrom(3), Z=8, D-calc = 1.702 g cm(-3); R = 0.0411, R(w) = 0.0447 for 5622 observed reflections. The redox properties of 2 were explored by cyclic voltammetry in MeCN, which revealed the presence of a reversible one-electron reduction process (bpcd based) and an irreversible oxidation (metal based). The nature of the HOMO and LUMO in 2 has been examined by carrying out extended Huckel MO calculations on the model cluster Ru-3(CO)(7)(H-4-bpcd)(mu(3)-S)(2), and the results are discussed relative to the observed electrochemistry.

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Documento generato il 27/11/20 alle ore 23:56:21