Synthetic applications of (Me3SiNSN)2E (E = S, Se) in chalcogen-nitrogen chemistry: formation and structural characterization of Cl2TeESN2 (E = S, Se) and [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, Br)

Jari Konu; Markku Ahlgrén; Stephen M Aucott; Tristram Chivers; Sophie H Dale; Mark R J Elsegood; Kathryn E Holmes; Sarah L M James; Paul F Kelly; Risto S Laitinen

doi:10.1021/ic050261f

Synthetic applications of (Me3SiNSN)2E (E = S, Se) in chalcogen-nitrogen chemistry: formation and structural characterization of Cl2TeESN2 (E = S, Se) and [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, Br)

Inorg Chem. 2005 Jul 11;44(14):4992-5000. doi: 10.1021/ic050261f.

Authors

Jari Konu¹, Markku Ahlgrén, Stephen M Aucott, Tristram Chivers, Sophie H Dale, Mark R J Elsegood, Kathryn E Holmes, Sarah L M James, Paul F Kelly, Risto S Laitinen

Affiliation

¹ Department of Chemistry, University of Oulu, P.O. Box 3000, 90014 University of Oulu, Finland.

PMID: 15998027
DOI: 10.1021/ic050261f

Abstract

The reaction of (Me3SiNSN)2S with TeCl4 in CH2Cl2 affords Cl2TeS2N2 (1) and that of (Me3SiNSN)2Se with TeCl4 produces Cl2TeSeSN2 (2) in good yields. The products were characterized by X-ray crystallography, as well as by NMR and vibrational spectroscopy and EI mass spectrometry. The Raman spectra were assigned by utilizing DFT molecular orbital calculations. The pathway of the formation of five-membered Cl2TeESN2 rings by the reactions of (Me3SiNSN)2E with TeCl4 (E = S, Se) is discussed. The reaction of (Me3SiNSN)2Se with [PPh4]2[Pd2X6] yields [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, 4a; Br, 4b), the first examples of complexes of the (Se2N2S)2- ligand. In both cases, this ligand bridges the two palladium centers through the selenium atoms.