{"title":"Oxidative Addition of Alkyl Iodides to [Sn(NMe2)2]2: In Situ Generation of RSn(NMe2)3 Compounds","authors":"David M. Ermert*, and , Milan Gembicky, ","doi":"10.1021/acs.organomet.4c00096","DOIUrl":null,"url":null,"abstract":"<p >Treatment of [Sn(NMe<sub>2</sub>)<sub>2</sub>]<sub>2</sub> (<b>1</b>) with R–I (where R = Et, <sup>i</sup>Pr, Me<sub>3</sub>SiCH<sub>2</sub>, F<sub>3</sub>CH<sub>2</sub>C, and F<sub>3</sub>C) yields the monoalkyltin amides (RSn(NMe<sub>2</sub>)<sub>3</sub>) (<b>3</b>–<b>7</b>) and the stannous iodide/amide dimer [ISn(NMe<sub>2</sub>)]<sub>2</sub> (<b>2</b>) as major products. The monoalkyl stannic amides (<b>3</b>–<b>7</b>) are light-sensitive liquids which are sufficiently volatile (<1% residual mass by TGA) for use as ALD/CVD precursors. The oxidative addition of R–I to a Sn(II) center, followed by exchange of a stannic iodide with unreacted <b>1</b>, is supported by the solid-state structural analysis of crystalline [<sup>i</sup>PrSn(NMe<sub>2</sub>)<sub>2</sub>I]<sub>2</sub> (<b>9</b>) and [ISn(NMe<sub>2</sub>)]<sub>2</sub> (<b>2</b>). The stannous iodide byproduct (<b>2</b>) is independently synthesized from stoichiometric amounts of SnI<sub>2</sub> and [Sn(NMe<sub>2</sub>)<sub>2</sub>]<sub>2</sub>. Heating solutions of <sup>i</sup>PrSn(NMe<sub>2</sub>)<sub>3</sub> (<b>4</b>) and <sup>i</sup>Pr–I produces nominal quantities (∼10%) or N<sup>i</sup>PrMe<sub>2</sub> and <b>9</b>; demonstrating RSn(NMe<sub>2</sub>)<sub>3</sub> sensitivity toward alkyl iodides via Sn(IV)–NMe<sub>2</sub> bond cleavage. The modified synthesis and light-sensitivity of [Sn(NMe<sub>2</sub>)<sub>2</sub>]<sub>2</sub> (<b>1</b>) are also discussed. Multinuclear NMR, solid-state structural analysis, and thermogravimetric differential scanning calorimetry (TGA-DSC) experiments are described.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00096","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Treatment of [Sn(NMe2)2]2 (1) with R–I (where R = Et, iPr, Me3SiCH2, F3CH2C, and F3C) yields the monoalkyltin amides (RSn(NMe2)3) (3–7) and the stannous iodide/amide dimer [ISn(NMe2)]2 (2) as major products. The monoalkyl stannic amides (3–7) are light-sensitive liquids which are sufficiently volatile (<1% residual mass by TGA) for use as ALD/CVD precursors. The oxidative addition of R–I to a Sn(II) center, followed by exchange of a stannic iodide with unreacted 1, is supported by the solid-state structural analysis of crystalline [iPrSn(NMe2)2I]2 (9) and [ISn(NMe2)]2 (2). The stannous iodide byproduct (2) is independently synthesized from stoichiometric amounts of SnI2 and [Sn(NMe2)2]2. Heating solutions of iPrSn(NMe2)3 (4) and iPr–I produces nominal quantities (∼10%) or NiPrMe2 and 9; demonstrating RSn(NMe2)3 sensitivity toward alkyl iodides via Sn(IV)–NMe2 bond cleavage. The modified synthesis and light-sensitivity of [Sn(NMe2)2]2 (1) are also discussed. Multinuclear NMR, solid-state structural analysis, and thermogravimetric differential scanning calorimetry (TGA-DSC) experiments are described.
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.