Reactivity of a Bis(alkynyl)-Vinylidene Osmium Complex: Access to Carbynes, Vinyl Ester Derivatives, and C–C and C–N Bond-Forming Reactions

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-22 DOI:10.1021/acs.organomet.6c00277

Sheila G. Curto, Joaquín M. Granados, Enrique Oñate, Montserrat Oliván

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引用次数: 0

Abstract

Hexahydride OsH₆(PⁱPr₃)₂ (1) reacts with tert-butylacetylene to yield bis(alkynyl)-vinylidene Os(C≡C^tBu)₂(=C=CH^tBu)(PⁱPr₃)₂ (2). Subsequent protonation of 2 with HOTf or Et₃N·3HF affords the bis(alkynyl)-carbyne derivatives [Os(C≡C^tBu)₂(≡CCH₂^tBu)(PⁱPr₃)₂]OTf (3) and OsF(C≡C^tBu)₂(≡CCH₂^tBu)(PⁱPr₃)₂ (4), respectively. In contrast, treatment of 2 with acetic acid leads to the alkynyl-vinylidene-vinyl ester derivative Os(C≡C^tBu){κ²-O,C-OC(CH₃)OC=CH^tBu}(=C=CH^tBu)(PⁱPr₃)₂ (5). Density functional theory (DFT) calculations, together with deuterium labeling experiments, demonstrate that the protonation may occur either at the C_β carbon of the vinylidene ligand or at the C_β carbon atom of one of the alkynyl groups, and that the formation of 5 is governed by thermodynamic control. The reaction of 2 with 2-aminopyridine provides a new route for the selective synthesis of a 2,3-disubstituted imidazo[1,2-a]pyridine derivative starting from tert-butylacetylene and 2-aminopyridine.

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双炔基-偏乙烯锇配合物的反应性：碳炔、乙烯基酯衍生物及C-C和C-N键形成反应

六氢化物OsH6(PiPr3)2(1)与叔丁基乙炔反应生成双（炔基）-偏乙烯Os(C≡CtBu)2(=C=CHtBu)(PiPr3)2(2)。随后，2与Et3N·3HF的hotf质子化得到双炔基羰基衍生物[Os(C≡CtBu)2(≡CCH2tBu)(PiPr3)2]OTf(3)和OsF(C≡CtBu)2(≡CCH2tBu)(PiPr3)2(4)。相反，用乙酸处理2则会得到炔基乙烯基乙烯基酯衍生物os (C≡CtBu){κ2-O,C-OC(CH3)OC=CHtBu}(=C=CHtBu)(PiPr3)2(5)。密度泛函理论（DFT）计算和氘标记实验表明，质子化可能发生在偏乙烯配体的c - β碳上，也可能发生在炔基的c - β碳原子上，并且5的形成受热力学控制。2与2-氨基吡啶的反应为从叔丁基乙炔和2-氨基吡啶开始选择性合成2,3-二取代咪唑[1,2-a]吡啶衍生物提供了新的途径。

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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.