Organometallic Chemistry b609350g有机金属化学.pdfVIP

Organo-transition metal cluster complexes Mark G. Humphrey* and Marie P. Cifuentes* DOI: 10.1039/b609350g 1 Introduction This chapter covers the chemistry of metal carbonyl and organometallic clusters containing three or more metal atoms. The treatment is in Periodic Group order, homometallic compounds being followed by heterometallic clusters. Ligands are not shown for high-nuclearity clusters, emphasis being placed on core geometry. 2 Spectroscopic studies The first gas-phase infrared spectra of a range of anionic iron clusters ([Fe (CO) ] 3 10 to [Fe (CO) ]) have been reported. Spectral data of this type were combined with 5 14 DFT calculations for smaller complexes ([Fe(CO) ], [Fe (CO) ], [Fe (CO) ]) to 4 2 7 2 8 obtain structural information for the cluster anions.1 Spectroelectrochemical and computational studies on the reversible two-electron reduction of bis(alkynyl) clusters Ru 2 (m -Z -RC R) (m-CO)(CO) show the first-formed product, which 4 4 2 2 10 contains a square-planar metal core with the alkyne ligands coordinated to opposite faces, quickly isomerizes to a thermodynamically more stable product where the alkyne ligands lie parallel to each other across the metal framework.2 Quantitative IR analysis of Rh (m-CO) (CO) , combined with deconvolution techniques, has been 4 3 9 used to obtain a spectrum of the all-terminal CO complex Rh (CO) , even though it 4 12 constitutes only ca. 1% of the sample.3 Laser desorption time-of-flight