Flash Communication: A Ferrous Adduct of a Phosphanylidene-σ4-phosphorane

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-09-10 DOI:10.1021/acs.organomet.4c0032910.1021/acs.organomet.4c00329

Ethan Zars, Matthew R. Mena, Michael R. Gau and Daniel J. Mindiola*,

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引用次数: 0

Abstract

The sterically encumbered phosphanylidene-σ⁴-phosphorane Mes*PPMe₃ (Mes* = 2,4,6-^tBu₃C₆H₂) smoothly displaces Et₂O in [(^tBupyrr₂py)Fe(OEt₂)] (1-OEt₂) (^tBupyrr₂py^2– = 3,5-^tBu₂-bis(pyrrolyl)pyridine) to form a rare example of a η¹-phospha-Staudinger adduct of Fe, namely, [(^tBupyrr₂py)Fe(Mes*PPMe₃)] (1-Mes*PPMe₃) in 64% yield. Complex 1-Mes*PPMe₃ is a ferrous, S = 2 system and quite thermally stable, but in the presence of B(C₆F₅)₃ and photolysis, it forms the phosphaindan ferrous adduct [(^tBupyrr₂py)Fe(phosphaindan)] (1-phosphaindan) (phosphaindan = HPCH₂C(Me₂)-2,4-^tBu₂C₆H₂) along with Me₃PB(C₆F₅)₃. In the absence of Lewis acid, photolysis of 1-Mes*PPMe₃ results instead in the formation of free phosphaindan and the PMe₃ ferrous adduct [(^tBupyrr₂py)Fe(PMe₃)] (1-PMe₃) thus suggesting that dissociation of the phosphanylidene-σ⁴-phosphorane precedes the formation of a transient phosphinidene fragment Mes*P. All phosphorus adducts of 1 were crystallographically characterized and show quite similar Fe–P distances (2.4685(5) for 1-Mes*PPMe₃; 2.5062(7) for 1-phosphaindan; and 2.4323(8) Å for 1-PMe₃).

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闪电通讯：亚磷酰σ4-磷烷的亚铁加合物

立体包被的亚膦酰-σ4-磷烷 Mes*PPMe3 （Mes* = 2,4,6-tBu3C6H2）顺利取代了 [(tBupyrr2py)Fe(OEt2)]（1-OEt2）（tBupyrr2py2- = 3、5-tBu2-双(吡咯基)吡啶)中形成一种罕见的 η1-phospha-Staudinger 加合物，即[(tBupyrr2py)Fe(Mes*PPMe3)]（1-Mes*PPMe3），收率为 64%。络合物 1-Mes*PPMe3 是一个亚铁、S = 2 体系，热稳定性相当高，但在 B(C6F5)3 和光解作用下，它会与 Me3PB(C6F5)3 一起形成磷丹亚铁加合物[(tBupyrr2py)Fe(phosphaindan)]（1-phosphaindan）（磷丹 = HPCH2C(Me2)-2,4-tBu2C6H2）。在没有路易斯酸的情况下，1-Mes*PPMe3 的光解反而会形成游离的磷丹和 PMe3 亚铁加合物[(tBupyrr2py)Fe(PMe3)]（1-PMe3），这表明在形成瞬时亚膦片段 Mes*P 之前，亚膦-σ4-磷烷已经解离。1 的所有磷加合物都具有晶体学特征，并显示出非常相似的铁-磷距离（1-Mes*PPMe3 为 2.4685(5)；1-phosphaindan 为 2.5062(7)；1-PMe3 为 2.4323(8) Å）。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.