Experimental and theoretical studies on 1,4,5,7-dithiadiazepinyl radicals: preparation and X-ray structure of 5-(trimethylsilyl)tetrachlorobenzo-1,4,5,7-dithiadiazepine

Chandrasekhar, Vadapalli ; Chivers, Tristram ; Parvez, Masood ; Vargas-Baca, Ignacio ; Ziegler, Tom (1997) Experimental and theoretical studies on 1,4,5,7-dithiadiazepinyl radicals: preparation and X-ray structure of 5-(trimethylsilyl)tetrachlorobenzo-1,4,5,7-dithiadiazepine Inorganic Chemistry, 36 (21). pp. 4772-4777. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic970230n

Related URL: http://dx.doi.org/10.1021/ic970230n

Abstract

1,4,5,7-Dithiadiazepinyl radicals and their selenium analogs have been studied by density functional theory calculations. Compared to 1,2,3,5-dithiadiazolyls, this novel family of 9 π -electron radicals is predicted to have low disproportionation and dimerization energies, properties that are advantageous for the preparation of molecular conductors. The radical [CH3C6H3S2N2C(C6H4CH3-4)]· (5a) was generated in solution by the cyclocondensation reaction of CH3C6H3(SCl)2 with 4-CH3C6H4CN2(SiMe3)3 followed by treatment with PhSeCl. The ESR spectrum of 5a consists of a slightly asymmetric quintet (g = 2.0070 and AN(iso) = 4.9 G). The N-(trimethylsilyl)-substituted precursor S(C6Cl4)S(NSiMe3)(4-CH3C6H4C)=N(6c) was characterized by X-ray crystallography: monoclinic, P21/a, a = 12.585(3) Å, b = 12.211(2) Å, c = 14.003(2) Å, β = 101.86(2)° , V = 2106.0(7) Å3, and Z = 4. Polycyclocondensation reactions and thermal instability toward elimination of nitriles hamper the isolation of pure samples of the radicals.

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