Organometallic Chemistry b609347g有机金属化学.pdfVIP

Group 14: silicon, germanium, tin and lead Richard A. Layfield DOI: 10.1039/b609347g 1. Introduction Rather than providing an exhaustive survey of Group 14 organometallic chemistry published in 2004–2005, this chapter takes the form of a ‘highlight’ review and will focus primarily on low-coordinate, multiply bonded organo-derivatives of silicon, germanium, tin and lead. Transition metal complexes in which Group 14 elements are present as ligands in a formally subvalent form will be described but ligands of the tetryl type (e.g. R3Si, silyl) are omitted. Naked cluster species, in which supporting organic ligands are absent, are also not covered by this review. 2. A silicon-silicon triple bond In recent editions of Specialist Periodical Reports, this chapter has begun with summaries of unsuccessful attempts to synthesize and structurally authenticate the silicon-silicon triple bond. It seems fitting, therefore, that the current review should open on a more positive note since in 2004 the elusive disilyne was finally reported by Sekiguchi and co-workers.1 Thus, a stable compound containing two 2-coordinate silicon centres can be prepared and isolated according to Scheme 1 Scheme 1 Green crystals of compound 1 are stable up to 100 1C and the silicon-silicon ˚ distance is 2.0622(9) A. An interesting structural feature that contrasts with the analogous carbon compounds is the significant degree of bending at the disilyne silicons, resulting in a bond angle of 137.44(4)1. The 29Si NMR spectrum of 1 reveals that the sp-hybridized silicons have a chemical shift of 89.9 ppm and hence are shielded relative to the chemical shift values typical of disilenes, R Si SiR . Additional support 2 Q 2 for the claim of a genuine triple bo