Complexes of Bidentate Phosphane Selenide Ligands with Mesitylenetellurenyl Iodide and with Tellurium Diiodide

• Published in: European Journal of Inorganic Chemistry 2006-03, Vol.2006 (6), p.1294-1302
• Main Authors: Hrib, Cristian G., Jones, Peter G., du Mont, Wolf-W., Lippolis, Vito, Devillanova, Francesco A.
• Format: Article
• Language: English
• Subjects: Heteronuclear NMR; Phosphane selenides; Raman spectroscopy; Soft-soft interactions; Tellurium iodides
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200500843

Bis(diphenylphosphanyl)methane diselenide (dppmSe2, 1) and bis(diphenylphosphanyl)ethane diselenide (dppeSe2, 2) reacted with 2 equiv. Br2 or I2 to form the insoluble solid products, dppm(SeX2)2 (X = Br, 3; X = I, 4) and dppe(SeX2)2 (X = Br, 5; X = I, 6). However, using the iodine‐like electrophile mesitylenetellurenyl iodide (MesTeI, 7), fairly soluble complexes, dppmSe2[Te(I)Mes]2 (8) and dppeSe2[Te(I)Mes]2 (9), were obtained. Complexes 8 and 9 contain two T‐shaped (10‐Te‐3) Se–Te(Mes)–I moieties bridged by dppm or dppe; solid 9 exhibits intermolecular soft–soft interactions between approximately linear Se–Te–I units. In a side reaction accompanying the crystallisation of complex 8, or by the reaction of 1 with Te and I2, a chelate complex dppmSe2TeI2 (10) was formed. Fortuitously, a crystal of the related compound dppeSe2TeI2 (11) was also obtained. In 10, a square planar cis‐Se2TeI2 group is part of a six‐membered ring, and 11 is a coordination polymer with trans‐Se2TeI2 moieties bridged by dppe. Averaged 31P‐ and 77Se NMR signals including 77Se–31P couplings, together with broad 125Te NMR singlets indicate phosphane selenide ligand exchange in solution, that is, the kinetically labile behaviour of complexes 8 and 9. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)