High-Nuclearity Carbonyl Clusters: Their Synthesis and Reactivity
1986; Elsevier BV; Linguagem: Inglês
10.1016/s0898-8838(08)60241-x
ISSN1557-8917
AutoresMaria D. Vargas, J. Nicola Nicholls,
Tópico(s)Inorganic Chemistry and Materials
ResumoThis chapter discusses the synthesis and reactivity of high-nuclearity carbonyl clusters (HNCC). The chapter defines HNCC as homo- or heteronuclear carbonyl clusters of transition and main group metals containing five or more metal atoms, each of which is linked to the metal core by at least one M—M bond. The chapter discusses the chemistry of the HNCC in terms of reaction type rather than metal by metal. All the HNCC that have been characterized to date by X-ray crystallographybare listed in a table together with the methods used for their synthesis and references to their spectroscopic data. Synthetic methods used for the preparation of HNCC may be classified in to two broad categories, depending on whether or not they involve the use of redox conditions; they are—syntheses not involving redox conditions and syntheses requiring reducing or oxidizing conditions. The synthesis of HNCC by redox condensation involves the reaction of an anionic mononuclear or polynuclear carbonyl species with a neutral, cationic, or even anionic fragment. A relatively small number of HNCC have been synthesized by oxidation of other carbonyl clusters. The oxidation reactions of a number of large carbide clusters have been found to provide relatively selective synthetic routes to clusters of reduced nuclearity. Oxidation of HNCC often results in cluster fragmentation or, as a consequence of redox condensation. X-Ray diffraction has often been successful in the determination of hydrogen atom position in HNCC hydrides.
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