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Science 22 August 2008:
Vol. 321. no. 5892, pp. 1069 - 1071
DOI: 10.1126/science.1160768
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Reports

A Stable Silicon(0) Compound with a Si=Si Double Bond

Yuzhong Wang, Yaoming Xie, Pingrong Wei, R. Bruce King, Henry F. Schaefer, III, Paul von R. Schleyer,* Gregory H. Robinson*

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si–Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 ± 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si–Si(Cl):L and L:Si=Si:L.

Department of Chemistry and Center for Computational Chemistry, The University of Georgia, Athens, GA 30602–2556, USA.

* To whom correspondence should be addressed. E-mail: schleyer{at}chem.uga.edu (P.v.R.S.); robinson{at}chem.uga.edu (G.H.R.)

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Science. ISSN 0036-8075 (print), 1095-9203 (online)