ESR Investigations of the Radicals {Li(3)[E(N(t)Bu)(3)](2)}(*) (E = S, Se) and the Radical Anions SO(x)()(N(t)Bu)(3)(-)(x)()(*)(-) (x = 1, 2)

Justin K. Brask; Tristram Chivers; Bruce McGarvey; Gabriele Schatte; Raymond Sung; René T. Boeré

doi:10.1021/ic9803560

ESR Investigations of the Radicals {Li(3)[E(N(t)Bu)(3)](2)}() (E = S, Se) and the Radical Anions SO(x)()(N(t)Bu)(3)(-)(x)()()(-) (x = 1, 2)

Inorg Chem. 1998 Sep 7;37(18):4633-4636. doi: 10.1021/ic9803560.

Authors

Justin K. Brask¹, Tristram Chivers, Bruce McGarvey, Gabriele Schatte, Raymond Sung, René T. Boeré

Affiliation

¹ Department of Chemistry, University of Calgary, Calgary, Alberta, Canada T2N 1N4, Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, Canada N9B 3P4, and Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, Alberta, Canada T1K 3M4.

PMID: 11670613
DOI: 10.1021/ic9803560

Abstract

The air oxidation of the cluster compounds [Li(2)E(N(t)Bu)(3)](2) (E = S, Se) in toluene produces deep blue (E = S) or green (E = Se) solutions. The ESR spectra of these solutions consist of a septet (1:3:6:7:6:3:1) of decuplets. The simulation of these spectra shows that the secondary hyperfine splitting results from interaction of the unpaired electron with three equivalent (7)Li ions consistent with the formation of the neutral radicals {Li(3)[E(N(t)Bu)(3)](2)}(*) (4a, E = S, g = 2.0039, a((14)N) = 5.69 G, a((7)Li) = 0.82 G; 4b, E = Se, g = 2.00652, a((14)N) = 5.41 G, a((7)Li) = 0.79 G). Over a period of 25 h the seven line pattern of 4b is replaced first by a five line (1:2:3:2:1) spectrum (g = 2.009, a((14)N) = 13.4 G) and, subsequently, by a three line (1:1:1) spectrum (g = 2.00946, a((14)N) = 15.4 G, a((77)Se) = 4.3 G), neither of which exhibit (7)Li hyperfine splitting. These spectra are tentatively assigned to the radical anions SeO(N(t)Bu)(2)(*)(-) and SeO(2)(N(t)Bu)(*)(-), respectively. The cluster {Li(2)[O(2)S(N(t)Bu)]}(n)() (3) is prepared by the reaction of sulfur dioxide with 2 equiv of LiNH(t)Bu in toluene. The air oxidation of toluene solutions of {Li(2)[OS(N(t)Bu)(2)]}(6) (2a) or 3 produces deep blue species. In the former case the initial ESR spectrum is a 1:2:3:2:1 quintet (g = 2.009, a((14)N) = 13.3 G) which, after 16 h, evolves into a 1:1:1 triplet (g = 2.0088, a((14)N) = 15.9 G). The same triplet is observed in the ESR spectrum of oxidized solutions of 3 leading to the assignments OS(N(t)Bu)(2)(*)(-) and O(2)S(N(t)Bu)(*)(-) for the quintet and triplet, respectively. The disproportionation 2OS(N(t)Bu)(2)(*)(-) --> O(2)S(N(t)Bu)(*)(-) + S(N(t)Bu)(3)(*)(-) is indicated by the changes observed for the ESR spectra of oxidized solutions of 2a.