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Titolo:
REACTION OF FCCCO(3)(CO)(9) WITH 2,3-BIS(DIPHENYLPHOSPHINO)MALEIC ANHYDRIDE (BMA) - X-RAY-DIFFRACTION STRUCTURE AND REDOX PROPERTIES OF (2)ETA(1)-C(FC)C=C(PPH(2))C(O)OC(O)](MU(2)-PPH(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: 1-2, volume: 250, anno: 1996,
pagine: 195 - 202
SICI:
0020-1693(1996)250:1-2<195:ROFW2A>2.0.ZU;2-K
Fonte:
ISI
Lingua:
ENG
Soggetto:
PARAMAGNETIC ORGANOMETALLIC MOLECULES; TRICOBALT CARBON CLUSTER; ALKYLIDYNETRICOBALT NONACARBONYL COMPLEXES; MIXED METAL-CLUSTERS; ELECTRON-TRANSFER; CRYSTAL-STRUCTURES; ALKYNE FUNCTIONALITY; TETRAHEDRANE CLUSTER; LIGAND SUBSTITUTION; PHCCO3(CO)9;
Keywords:
CRYSTAL STRUCTURES; REDOX PROPERTIES; COBALT COMPLEXES; ALKYLIDYNE-CAPPED COMPLEXES; CLUSTER COMPLEXES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
87
Recensione:
Indirizzi per estratti:
Citazione:
H.F. Shen et al., "REACTION OF FCCCO(3)(CO)(9) WITH 2,3-BIS(DIPHENYLPHOSPHINO)MALEIC ANHYDRIDE (BMA) - X-RAY-DIFFRACTION STRUCTURE AND REDOX PROPERTIES OF (2)ETA(1)-C(FC)C=C(PPH(2))C(O)OC(O)](MU(2)-PPH(2))", Inorganica Chimica Acta, 250(1-2), 1996, pp. 195-202

Abstract

The reaction between the tricobalt cluster FcCCo(3)(CO)(9) (1) (whereFc=ferrocenyl) and the redox-active diphosphine ligand 2,3-bis (diphenylphosphino) maleic anhydride (bma) affords the new cluster Co-3(CO)(6)[mu(2)-eta(2):eta(1)-C(Fc)C=C(PPh(2)) C(O)OC(O)](mu(2)-PPh(2)) (3) in refluxing 1,2-dichloroethane or toluene. The cluster FcCCo(3)(CO)(7)(bma) (2), a logical precursor to 3, was observed in solution by IR spectroscopy when cluster 1 and bma were refluxed in the low boiling point solvent CH2Cl2; however, putative 2 could not be isolated due to its rapid conversion to the final product 3. Cluster 3 has been fully characterized in solution by IR and NMR (C-13 and P-31) spectroscopy andin the solid state by X-ray diffraction analysis. ):eta(1)-C(Fc)C=C(PPh(2))C(O)OC(O)](mu(2)-PPh(2)), as the CH2Cl2 Solvate, crystallized inthe triclinic space group P (1) over bar, a=10.4704(6), b=14.6033(8),c=14.787(1) Angstrom, alpha=102.973(5), beta=94.517(8), gamma=90.197(5)degrees, V=2195.9(2) Angstrom(3), Z=2, D-calc=1.653 g cm(-3); R=0.0411, R(w)=0.0449 for 3602 observed reflections with I>3 sigma(I). Cyclic voltammetric investigations of 3 in CH2Cl2 reveal the presence of three reversible redox responses assigned to the 0/1(+), 0/1(-), and 1(-)/2(-) redox couples. The nature of the HOMO and the two lowest unoccupied molecular orbitals (LUMO and SUMO) in 3 has been determined by carrying out extended Huckel calculations on the model compound Co-3(Co)(6)[mu(2) eta(2):eta(1)-C(Fc)C=C(PH2)C(O)O](mu(2)-PH2), the results ofwhich are discussed relative to the observed electrochemistry of 3 and related cluster compounds.

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Documento generato il 27/11/20 alle ore 21:09:43