Neben Marc C, Wegerich Nils, Al Said Tarek A, Thompson Richard R, Demeshko Serhiy, Dollberg Kevin, Tkach Igor, Van Trieste Gerard P, Verplancke Hendrik, von Hänisch Carsten, Holthausen Max C, Powers David C, Schnegg Alexander, Schneider Sven
Institut für Anorganische Chemie and International Center for Advanced Studies of Energy Conversion, Georg-August-Universität Göttingen, Tammannstr 4, 37077 Göttingen, Germany.
Institut für Anorganische und Analytische Chemie Goethe-Universität, Max-von-Laue-Strasse7, 60438 Frankfurt am Main, Germany.
J Am Chem Soc. 2025 Feb 12;147(6):5330-5339. doi: 10.1021/jacs.4c16830. Epub 2025 Jan 29.
Nitrenes (R-N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity of this important class of transient intermediates has been attributed to their electronic structures, particularly the accessibility of triplet vs singlet states. In contrast, electronic structure trends along the heavier pnictinidene analogues (R-Pn; Pn = P-Bi) are much less systematically explored. We here report the synthesis of a series of metallodipnictenes, {M-Pn═Pn-M} (M = Pd, Pt; Pn = P, As, Sb, Bi) and the characterization of the transient metallopnictinidene intermediates, {M-Pn} for Pn = P, As, Sb. Structural, spectroscopic, and computational analysis revealed spin triplet ground states for the metallopnictinidenes with characteristic electronic structure trends along the series. In comparison to the nitrene, the heavier pnictinidenes exhibit lower-lying ground state SOMOs and singlet excited states, thus suggesting increased electrophilic reactivity. Furthermore, the splitting of the triplet magnetic microstates is beyond the phosphinidenes {M-P} dominated by heavy pnictogen atom induced spin-orbit coupling.
氮宾（R-N）已经受到了大量实验和理论研究。这类重要的瞬态中间体的基本反应活性归因于它们的电子结构，特别是三线态与单线态的可及性。相比之下，对于较重的磷族元素类似物（R-Pn；Pn = P - Bi）的电子结构趋势的系统性研究则少得多。我们在此报告了一系列金属二磷族元素化合物{M-Pn═Pn-M}（M = Pd，Pt；Pn = P，As，Sb，Bi）的合成以及瞬态金属磷族元素中间体{M-Pn}（Pn = P，As，Sb）的表征。结构、光谱和计算分析揭示了金属磷族元素的三线态基态以及该系列具有特征性的电子结构趋势。与氮宾相比，较重的磷族元素表现出能量较低的基态单占据分子轨道和单线态激发态，因此表明亲电反应活性增强。此外，三线态磁微态的分裂超出了由重磷族原子诱导的自旋 - 轨道耦合主导的膦亚基{M-P}。
