Kinetic Stabilization in Diaryl-Substituted Stannylenes: N2O Reactivity, Intramolecular C–H Activation, and Crystalline (Eind)Li(THF)2 as a Versatile Precursor in Tin Chemistry

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-07-21 DOI:10.1021/acs.organomet.5c00203

Miray Aklan, Jonathan Kieselbach, Christopher Golz and Malte Fischer*,

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引用次数: 0

Abstract

The reactivity of the kinetically stabilized stannylene (^MesTer)₂Sn (1) (^MesTer = –C₆H₃-2,6-(2,4,6-Me₃-C₆H₂)₂) toward N₂O is revisited, yielding the terminal tin(IV) hydroxide 2 via formal intramolecular C(sp³)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)₂ (3) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)₂Sn (4). Compound 4 can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (6). Both 4 and 6 serve as suitable precursors for the synthesis of the heteroleptic s-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe₃)₂} (5).

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二芳基取代锡炔的动力学稳定：N2O反应活性、分子内C-H活化和晶体（末端）Li(THF)2作为锡化学中的通用前驱体

重新考察了动力学稳定的锡炔（MesTer）2Sn (1) （MesTer = - c6h3,3,6 -(2,4,6- me3 - c6h2)2）对N2O的反应活性，通过假定的末端锡酮中间体的分子内C(sp3) - h活化产生末端锡（IV）氢氧化物2。通过在锡中心切换到Eind连接（Eind = 1,1,3,3,5,5,7,7-辛乙基-s-羟基-4-基），报道了晶体锂盐（Eind）Li(THF)2(3)的合成和表征，作为清洁生成相应的锡炔（Eind）2Sn(4)的直接前体。化合物4可以进一步清晰地转化为杂电性的Eind/卤化物锡炔（Eind）SnCl(6)。4和6均可作为杂电性s-羟基-/酰胺取代锡炔（Eind）Sn{N(SiMe3)2}(5)的合适前驱体。

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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.