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Group 11 Complexes of the P,Te-Centered Ligand [TePiPr2NPiPr2]: Synthesis, Structures, and Insertion Reactions of the Copper(I) Complex with Chalcogens

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posted on 20.04.2009, 00:00 by Jamie S. Ritch, Tristram Chivers
The lithium reagent [LiTePiPr2NPiPr2] undergoes metathetical reactions with group 11 chlorides to give the complexes {M(TePiPr2NPiPr2)}3 (6: M = Cu; 7: M = Ag) and (Ph3P)Au(TePiPr2NPiPr2) (8) as yellow crystalline solids. These new complexes were characterized by single crystal X-ray diffraction and multinuclear NMR spectroscopy. The tellurium atoms in the trimeric complexes 6 and 7 occupy bridging positions to give a Cu3Te3 ring in a twist-boat conformation with short M···M contacts (M = Cu, Ag). Variable temperature 31P NMR and ESI-MS spectra for 6 and 7 give evidence for the formation of several oligomers in tetrahydrofuran solution. The reactions of 6 with dioxygen (or Me3NO), elemental sulfur, or red selenium generate the chalcogen-insertion products {Cu(TePiPr2NPiPr2E)}3 (9: E = O; 10: E = S; 11: E = Se), which were also structurally characterized by single crystal X-ray diffraction and multinuclear NMR spectroscopy. The lighter chalcogens are two-coordinate while the tellurium centers occupy bridging positions in the trimeric complexes 911 giving rise to Cu3Te3 rings in a chairlike conformation.

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