Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry
Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry
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DOI：
10.1002/anie.201707921
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发表时间：
2017-11-13
影响因子：
16.6
通讯作者：
Agapie, Theodor
中科院分区：
文献类型：
--
作者：
Buss, Joshua A.;Oyala, Paul H.;Agapie, Theodor
通过氯代二苯并-7-(3)-磷-冰片二烯的P原子和氯原子的基团转移，合成了端基的磷化钼。该化合物是第一个结构表征的具有d价电子的末端过渡金属磷化物。在四方配位场中，这些电子占据d(Xy)配位的轨道，这是一种既容纳金属d电子又容纳形式MP三键的电子构型。连续波(CW)和脉冲电子顺磁共振(EPR)表征证实了单电子氧化在P上形成了具有显著自旋密度的瞬时开壳末端磷化阳离子。该物种通过分子间磷化物偶联形成简单的P-P键。
A terminal Mo phosphide was prepared through the group transfer of both P and Cl atoms from chloro-substituted dibenzo-7 lambda(3)-phosphanorbornadiene. This compound represents the first structurally characterized terminal transitionmetal phosphide with valence d electrons. In the tetragonal ligand field, these electrons populate an orbital of d(xy) parentage, an electronic configuration that accommodates both metal d electrons and a formal M P triple bond. Single-electron oxidation affords a transient open-shell terminal phosphide cation with significant spin density on P, as corroborated by continuous wave (CW) and pulse electron paramagnetic resonance (EPR) characterization. Facile P-P bond formation occurs from this species through intermolecular phosphide coupling.