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Titolo:
Activation of alkynols on transition metal carbonyl clusters. Reactions of1-ethynylcyclohexanol with Fe-3(CO)(12) and Co-2(CO)(8). Crystal structures of Co-3(CO)(9)[mu(3)-CCH2(C6H10OH)], Fe-3(CO)(9)(mu-CO)[mu(3)-eta(2)-C=C(C6H10)] and Co2Fe(CO)(6)(mu-CO)[mu(3)-eta(7)-(C6H9)CC(H)C(H)C(H)(C6H10)]
Autore:
Gatto, E; Gervasio, G; Marabello, D; Sappa, E;
Indirizzi:
Univ Turin, IFM, Dipartimento Chim, I-10125 Turin, Italy Univ Turin Turin Italy I-10125 , Dipartimento Chim, I-10125 Turin, Italy Univ Piemonte Orientale, Dipartimento Sci & Tecnol Avanzate, I-15100 Alessandria, Italy Univ Piemonte Orientale Alessandria Italy I-15100 100 Alessandria, Italy
Titolo Testata:
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
fascicolo: 9, , anno: 2001,
pagine: 1485 - 1491
SICI:
1472-7773(2001):9<1485:AOAOTM>2.0.ZU;2-U
Fonte:
ISI
Lingua:
ENG
Soggetto:
X-RAY STRUCTURE; MOLECULAR-STRUCTURE; BOND-CLEAVAGE; SPECTROSCOPIC CHARACTERIZATION; BUTTERFLY CLUSTER; = H; COMPLEXES; RUTHENIUM; LIGANDS; TRANSFORMATION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
54
Recensione:
Indirizzi per estratti:
Indirizzo: Marabello, D Univ Turin, IFM, Dipartimento Chim, Via Pietro Giuria 7, I-10125 Turin, Italy Univ Turin Via Pietro Giuria 7 Turin Italy I-10125 in, Italy
Citazione:
E. Gatto et al., "Activation of alkynols on transition metal carbonyl clusters. Reactions of1-ethynylcyclohexanol with Fe-3(CO)(12) and Co-2(CO)(8). Crystal structures of Co-3(CO)(9)[mu(3)-CCH2(C6H10OH)], Fe-3(CO)(9)(mu-CO)[mu(3)-eta(2)-C=C(C6H10)] and Co2Fe(CO)(6)(mu-CO)[mu(3)-eta(7)-(C6H9)CC(H)C(H)C(H)(C6H10)]", J CHEM S DA, (9), 2001, pp. 1485-1491

Abstract

The reactions of Co-2(CO)(8) with 1-ethynylcyclohexanol (HC=CC6H10OH, ECY)in benzene led mainly to Co-2(CO)(6)(ECY) 1 and to smaller amounts of the methylidyne complex Co-3(CO)(9)[mu (3)-CCH2(C6H10OH)] 2. The reactions of Fe-3(CO)(12) with ECY in the same solvent led to binuclear metallacyclic derivatives Fe-2(CO)(6)(ECY)(2) (isomers 3a, 3b) or Fe-2(CO)(6)[(ECY)(2)-H2O] 3c as the main products; small yields of trinuclear complexes Fe-3(CO)(9)(mu -CO)[mu (3)-eta (2)-1,2-HC=C(C6H10OH)] 4 Fe-3(CO)(9)(mu -CO)[mu (3)-eta (2)-1,2-C=C(C6H10)] 5 and Fe-3(CO)(7)[mu (3)-eta (7)-(C6H10OH)CCHCHC(C6H9)] 6 {containing respectively a parallel alkynol, an allenylidene and a dimeric metallacyclic ligand} were also obtained, together with 7, a thermal decomposition product of 6. Finally, when Co-2(CO)(8) was treated with ECY in benzene, and Fe-3(CO)(12) was added, the heterometallic complex Co2Fe(CO)(6)(mu -CO)[mu (3)-eta (7)-(C6H9)CC(H)C(H)C(H)(C6H10)] 8 was obtained in low yields. The complexes have been characterized by means of IR and H-1 NMR spectroscopies and by mass spectrometry. The structures of 2, 5, 8 have been determined by X-ray diffraction. Complex 2 contains an "hydrogenated" ECY ligand, 5 an allenylidene ligand formed upon dehydration of ECY (loss of the OH and of the terminal hydrogen), whereas 8 contains a ligand formed by tail-to-tail coupling of two ECY molecules, with loss of water and oxygen and shift of hydrogen. The elemental analysis of complex 8 gave a Co:Fe ratio of 2:1; on the basis of this analysis, the refinement of the diffraction data allowed a hypothesis on the distribution of the metal atoms in the cluster. Reaction pathways for the formation of these clusters are proposed and dehydration mechanisms for the ligand discussed.

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Documento generato il 01/04/20 alle ore 11:47:55