Organometallics最新文献_第6页

Flash Communication: Metathesis of Heavy Alkyne Analogues in Solution via Dissociation of m-Terphenyl Substituted Distannynes and Diplumbynes 闪光通讯：通过间terphenyl取代的Distannynes和Diplumbynes的解离，在溶液中重炔类似物的再合成

IF 2.5 3区化学

Organometallics Pub Date : 2025-06-10 DOI: 10.1021/acs.organomet.5c0007410.1021/acs.organomet.5c00074

Joshua D. Queen*, and , Philip P. Power*,

{"title":"Flash Communication: Metathesis of Heavy Alkyne Analogues in Solution via Dissociation of m-Terphenyl Substituted Distannynes and Diplumbynes","authors":"Joshua D. Queen*,  and , Philip P. Power*, ","doi":"10.1021/acs.organomet.5c0007410.1021/acs.organomet.5c00074","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00074https://doi.org/10.1021/acs.organomet.5c00074","url":null,"abstract":"The terphenyl substituted distannynes and diplumbynes ArEEAr (E = Sn, Pb; Ar = AriPr4, C6H3-2,6-(C6H3-2,6-iPr2)2; Ar = AriPr6, C6H3-2,6-(C6H2-2,4,6-iPr3)2) undergo metathesis and ligand redistribution reactions in solution at ambient temperature to yield mixtures of asymmetrically substituted and heterometallic heavy alkyne analogues. The ambient temperature solution EPR spectrum of AriPr6SnSnAriPr6 shows a weak signal corresponding to the (SnAriPr6)· radical, and the thermolysis of AriPr8PbPbAriPr8 (AriPr8 = C6H-3,5-iPr2-2,6-(C6H2-2,4,6-iPr3)2) in toluene yields the plumbylene Pb(CH2C6H5)AriPr8, also suggesting that a transient Pb(AriPr8)· radical is liberated on heating. These results provide further evidence to the solution equilibria of the heavy group 14 analogues with the respective one-coordinate metal radicals.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 12","pages":"1229–1234 1229–1234"},"PeriodicalIF":2.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00074","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stereoselective Epoxidation of Unfunctionalized Aliphatic Alkenes with a Macrocyclic Tetra-NHC Iron(II) Catalyst 用大环四nhc铁（II）催化剂立体选择性环氧化非功能化脂肪烯烃

IF 2.5 3区化学

Organometallics Pub Date : 2025-06-10 DOI: 10.1021/acs.organomet.5c0018110.1021/acs.organomet.5c00181

Kevin M. Blatchford, Vernon H. Stafford III, Thomas D. Jones, Konstantinos D. Vogiatzis* and David M. Jenkins*,

{"title":"Stereoselective Epoxidation of Unfunctionalized Aliphatic Alkenes with a Macrocyclic Tetra-NHC Iron(II) Catalyst","authors":"Kevin M. Blatchford, Vernon H. Stafford III, Thomas D. Jones, Konstantinos D. Vogiatzis* and David M. Jenkins*, ","doi":"10.1021/acs.organomet.5c0018110.1021/acs.organomet.5c00181","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00181https://doi.org/10.1021/acs.organomet.5c00181","url":null,"abstract":"The development of atom-economical and earth-abundant catalysis for enantiopure epoxides is highly valuable since these strained chiral rings are key intermediates for many synthetic applications. However, one class of alkenes has remained particularly challenging for effective chiral catalysis: unfunctionalized aliphatic alkenes. Furthermore, despite epoxides’ significance, no catalyst for asymmetric epoxidation of unfunctionalized aliphatic alkenes has been developed using an iron complex as the catalyst and H2O2 as the oxidant. This combination of catalyst and oxidant is highly attractive due to the high terrestrial abundance of iron and the benign byproduct (water) from the oxidation reaction. This report showcases a C2-symmetric macrocyclic tetra-NHC iron(II) catalyst that is highly effective for epoxidation of cyclic and acyclic aliphatic alkenes, giving high yields and up to moderate %ee values while employing H2O2 as the oxidant. DFT analyses elucidate the free-energy pathway for the formation of the postulated iron-oxo intermediate as well as the key transition states for the induction of stereochemistry during the formation of the epoxide. Both the iron(II)/iron(IV)-oxo and iron(III)/iron(V)-oxo cycles were considered as possible pathways.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 12","pages":"1304–1313 1304–1313"},"PeriodicalIF":2.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Flash Communication: Metathesis of Heavy Alkyne Analogues in Solution via Dissociation of m‑Terphenyl Substituted Distannynes and Diplumbynes. 闪光通讯：通过间Terphenyl取代的Distannynes和Diplumbynes的解离，在溶液中重炔类似物的再合成。

IF 2.5 3区化学

Organometallics Pub Date : 2025-06-10 eCollection Date: 2025-06-23 DOI: 10.1021/acs.organomet.5c00074

Joshua D Queen, Philip P Power

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引用次数: 0

IF 2.5 3区化学