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.

Complexes of Bidentate Phosphane Selenide Ligands with Mesitylene Tellurenyl Iodide and with Tellurium Diiodide

LIPPOLIS, VITO;
2006-01-01

Abstract

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.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11584/14784
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