ISSN:
0009-2940
Keywords:
Metal atom synthesis
;
Clusters
;
Electrochemistry
;
Cyclic voltammetry
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Metal Atoms in the Synthesis of Metal Clusters, II1). - Reactions of Substituted Cyclopentadienes and Nickelocene with Nickel and Iron AtomsBy vaporizing nickel atoms into solutions of tert-butyl-substituted cyclopentadienes in methylcyclohexane mononuclear sandwich compounds (1, 4, and 6 as main products) as well as tri- and tetranuclear clusters are prepared. With mono- and di-tert-butyl-substituted cyclopentadienes as ligands the new clusters 2 and 5 are obtained. In the reaction with 1,2,4-tri-tert-butylcyclopentadiene 6 is the only observed product. Hindered rotation around the metal-ligand bond vector is observed for 4 even at room temperature. When treating 1 with nickel atoms cluster 2 is formed, indicating some importance of 1 during the formation of 2 in the above reaction. Clusters 2 and 5 contain hydrido ligands, which could be identified in the case of tris(1,3-di-tert-butyl-η5-cyclopentadienyl)trinickel dihydride (5) by a single crystal structure determination as μ3-H bridges. A tetrahedral structure is found for the cluster 2 by X-ray crystallography. With the aid of MS, IR, magnetic measurements, and cyclovoltammetric investigations 2 is identified as a mixture of 2a and 2b bearing one or three bridging hydrogens, respectively. In general 2a, 2b, and 5 show a rich redox chemistry with reversible redox couples between -2 and +2. Reaction of iron atoms, nickelocene, and mesitylene in methylcyclohexane at -120°C leads unexpectedly to cluster 3, tetrakis(η5-cyclopentadienyl)tetranickel trihydride and a not yet identified (η5-cyclopentadienyl)mesityleneiron complex. Possible formation routes for 1-6 are discussed.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240210
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