Abstract
The reaction of di-tert-butyldichlorosilane with lithium produced hepta-tert-butylcyclotetrasilane ( 1) and trans-1,1,2,3,3,4-hexa-tert-butylcyclotetrasilane ( 2). The structures of 1 and 2 were determined by X-ray crystallography. Crystal data for 1: orthorhombic, Cmcm, a = 12.071(1) A ̊ , b = 17.964(2) A ̊ , c = 18.292(1) A ̊ , V = 1534.6(2) A ̊ 3, Z = 4, R, 0.067, R w = 0.051 for 1160 reflections. Crystal data for 2: tetragonal, P4 2/m, a = 9.159(1) A ̊ , c = 18.292(1) A ̊ , V = 1534.6(2) A ̊ 3, Z = 2, R = 0.047, R w = 0.056 for 768 reflections. Compound 1 is a highly crowded molecule which contains unusually long SiSi bonds (2.542(2) Å) and a folded cyclotetrasilane ring with relatively small dihedral angles of 15.2° and 16.1°. In the UV spectrum of 1, absorption extends to the longer wavelength region than 2 and other alkyl-substituted cyclotetrasilanes so far reported. The oxidation potential of 1 (1.02 V vs. SCE) is significantly low compared with those of 2 and other less crowded cyclotetrasilanes.
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