Group 11 Complexes of the P,Te-Centered Ligand [TePiPr2NPiPr2]−: Synthesis, Structures, and Insertion Reactions of the Copper

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• 作者：Jamie S. Ritch ; Tristram Chivers
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：April 20, 2009
• 年：2009
• 卷：48
• 期：8
• 页码：3857-3865
• 全文大小：220K
• 年卷期：v.48,no.8(April 20, 2009)
• ISSN：1520-510X

文摘

The lithium reagent [LiTeP<sup>isup>Pr<sub>2sub>NP<sup>isup>Pr<sub>2sub>] undergoes metathetical reactions with group 11 chlorides to give the complexes {M(TeP<sup>isup>Pr<sub>2sub>NP<sup>isup>Pr<sub>2sub>)}<sub>3sub> (6: M = Cu; 7: M = Ag) and (Ph<sub>3sub>P)Au(TeP<sup>isup>Pr<sub>2sub>NP<sup>isup>Pr<sub>2sub>) (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 Cu<sub>3sub>Te<sub>3sub> ring in a twist-boat conformation with short M···M contacts (M = Cu, Ag). Variable temperature <sup>31sup>P 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 Me<sub>3sub>NO), elemental sulfur, or red selenium generate the chalcogen-insertion products {Cu(TeP<sup>isup>Pr<sub>2sub>NP<sup>isup>Pr<sub>2sub>E)}<sub>3sub> (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 9−11 giving rise to Cu<sub>3sub>Te<sub>3sub> rings in a chairlike conformation.