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PCP 桥联重杂中心单阴离子 [HC(PPh(2)E)(PPh(2))](-)（E = Se、Te）和 [HC(PR(2)E)(2)](-)（E = Se、Te、R = Ph；E = Se、R = (i)Pr）的结构和光谱研究：同核 12 族配合物和 [HC(PR(2)Se)(2)](-)的单电子氧化。

Structural and spectroscopic studies of the PCP-bridged heavy chalcogen-centered monoanions [HC(PPh(2)E)(PPh(2))](-) (E = Se, Te) and [HC(PR(2)E)(2)](-) (E = Se, Te, R = Ph; E = Se, R = (i)Pr): homoleptic Group 12 complexes and one-electron oxidation of [HC(PR(2)Se)(2)](-).

机构信息

Department of Chemistry, University of Calgary, 2500 University Drive N.W., Calgary, Alberta T2N 1N4, Canada.

出版信息

Inorg Chem. 2009 Dec 21;48(24):11788-98. doi: 10.1021/ic901878h.

DOI:10.1021/ic901878h
PMID:19928797
Abstract

Selenium- and tellurium-containing bis(diphenylphosphinoyl)methane monoanions were prepared by oxidation of the anion HC(PPh(2))(2) with elemental chalcogens. The selenium-containing isopropyl derivative was synthesized by generating [H(2)C(P(i)Pr(2))(2)] via a reaction between [H(2)C(PCl(2))(2)] and 4 equiv of (i)PrMgCl prior to in situ oxidation with selenium followed by deprotonation with LiN(i)Pr(2). The solid-state structures of the lithium salts of the monochalcogeno anions TMEDA.Li[HC(PPh(2)E)(PPh(2))] (E = Se (Li7a), E = Te (Li7b)) and the dichalcogeno anions TMEDA.Li[HC(PR(2)Se)(2)] (R = Ph (Li8a), (i)Pr (Li8c)) revealed five- and six-membered LiEPCP and LiSePCPSe rings, respectively. The homoleptic group 12 complexes {MHC(PPh(2)Se)(2)} (M = Zn (9a), Hg (9b)) were prepared from Li8a and MCl(2) and shown to have distorted-tetrahedral structures; the nonplanarity of the carbon center in the PC(H)P unit of the Zn complex 9a is attributed to crystal-packing effects. The complexes Li7a, Li7b, Li8a, TMEDA.Li[HC(PPh(2)Te)(2)] (Li8b), Li8c, 9a, and 9b were characterized in solution by multinuclear ((1)H, (7)Li, (13)C, (31)P, (77)Se, (125)Te, and (199)Hg) NMR spectroscopy. One-electron oxidation of Li8a and Li8c with iodine in a variety of organic solvents produced [H(2)C(PR(2)Se)(2)] (R = (i)Pr, Ph) as the final product, presumably owing to hydrogen abstraction from the solvent. DFT calculations revealed a significant contribution from the p orbital on carbon to the SOMO of the radicals HC(PR(2)Se)(2) (R = (i)Pr, Ph).

摘要

硒和碲双（二苯基膦酰基）甲烷单阴离子由元素硫属化合物氧化阴离子 [HC(PPh(2))(2)]-制得。含硒的异丙基衍生物通过 [H(2)C(PCl(2))(2)]与 4 当量的 (i)PrMgCl 反应生成 [H(2)C(P(i)Pr(2))(2)]，然后用硒原位氧化，再用 LiN(i)Pr(2)脱质子化制得。单核硫属阴离子 TMEDA.Li[HC(PPh(2)E)(PPh(2))]（E = Se（Li7a），E = Te（Li7b））和双核硫属阴离子 TMEDA.Li[HC(PR(2)Se)(2)]（R = Ph（Li8a），(i)Pr（Li8c））的锂盐的固态结构分别揭示了五元环和六元环 LiEPCP 和 LiSePCPSe。均配体 12 族金属配合物 {MHC(PPh(2)Se)(2)}（M = Zn（9a），Hg（9b））由 Li8a 和 MCl(2) 制备，并显示出扭曲四面体结构；Zn 配合物 9a 中 PC(H)P 单元的碳中心的非平面性归因于晶体堆积效应。配合物 Li7a、Li7b、Li8a、TMEDA.Li[HC(PPh(2)Te)(2)]（Li8b）、Li8c、9a 和 9b 在溶液中通过多核（（1）H、（7）Li、（13）C、（31）P、（77）Se、（125）Te 和（199）Hg）NMR 光谱进行了表征。用碘在各种有机溶剂中对 Li8a 和 Li8c 进行单电子氧化，得到最终产物 [H(2)C(PR(2)Se)(2)]（R = (i)Pr，Ph），这可能是由于溶剂的氢提取。DFT 计算表明，自由基 HC(PR(2)Se)(2)（R = (i)Pr，Ph）的最高占据轨道（SOMO）中碳的 p 轨道有很大贡献。

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