R. Joseph Lastowski, Vincent J. Flores, Laurent Souqui, John R. Abelson, Gregory S. Girolami
{"title":"作为化学气相沉积前驱体的 3-二甲基氨基-1-丙基螯合配体化合物。镍(II)、钯(II)和铂(II)的 M[(CH2)3NMe2]2配合物的合成与表征","authors":"R. Joseph Lastowski, Vincent J. Flores, Laurent Souqui, John R. Abelson, Gregory S. Girolami","doi":"10.1021/acs.organomet.4c00186","DOIUrl":null,"url":null,"abstract":"We describe the synthesis and characterization of three new square-planar compounds of stoichiometry M[(CH<sub>2</sub>)<sub>3</sub>NMe<sub>2</sub>]<sub>2</sub>, where M = Ni, Pd, or Pt, each of which contains two chelating 3-dimethylamino-1-propyl ligands. The nickel(II) and palladium(II) compounds decompose above −78 and 0 °C, respectively, but the platinum(II) compound has a thermolysis onset temperature of 130 °C. The Pd and Pt complexes are dynamic in solution: they undergo ring inversion with small free energies of activation of Δ<i>G</i><sup>⧧</sup> = 7.9 ± 0.1 and 8.3 ± 0.1 kcal mol<sup>–1</sup>, respectively, at 298 K. The Pt complex sublimes at 40 °C and 5 mTorr. In benzene solution, the Pt compound thermolyzes primarily through β-hydrogen elimination; 80 ± 10% of the hydrogen atoms and 75 ± 5% of the carbon atoms from the precursor can be accounted for in the byproducts. The thermolysis of the Pt complex in C<sub>6</sub>D<sub>6</sub> follows first-order kinetics, with an activation free energy Δ<i>G</i><sup>⧧</sup> of 29.9 ± 0.1 kcal mol<sup>–1</sup> at 110 °C. Under CVD conditions, thin films grown of the Pt complex at 200 °C contain nanocrystalline Pt; analysis of the film growth byproducts suggest that the main decomposition pathway involves β-hydrogen elimination and reductive elimination steps, as seen in solution.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Compounds with Chelating 3-Dimethylamino-1-propyl Ligands as Chemical Vapor Deposition Precursors. Synthesis and Characterization of M[(CH2)3NMe2]2 Complexes of Nickel(II), Palladium(II), and Platinum(II)\",\"authors\":\"R. Joseph Lastowski, Vincent J. Flores, Laurent Souqui, John R. Abelson, Gregory S. Girolami\",\"doi\":\"10.1021/acs.organomet.4c00186\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"We describe the synthesis and characterization of three new square-planar compounds of stoichiometry M[(CH<sub>2</sub>)<sub>3</sub>NMe<sub>2</sub>]<sub>2</sub>, where M = Ni, Pd, or Pt, each of which contains two chelating 3-dimethylamino-1-propyl ligands. The nickel(II) and palladium(II) compounds decompose above −78 and 0 °C, respectively, but the platinum(II) compound has a thermolysis onset temperature of 130 °C. The Pd and Pt complexes are dynamic in solution: they undergo ring inversion with small free energies of activation of Δ<i>G</i><sup>⧧</sup> = 7.9 ± 0.1 and 8.3 ± 0.1 kcal mol<sup>–1</sup>, respectively, at 298 K. The Pt complex sublimes at 40 °C and 5 mTorr. In benzene solution, the Pt compound thermolyzes primarily through β-hydrogen elimination; 80 ± 10% of the hydrogen atoms and 75 ± 5% of the carbon atoms from the precursor can be accounted for in the byproducts. The thermolysis of the Pt complex in C<sub>6</sub>D<sub>6</sub> follows first-order kinetics, with an activation free energy Δ<i>G</i><sup>⧧</sup> of 29.9 ± 0.1 kcal mol<sup>–1</sup> at 110 °C. Under CVD conditions, thin films grown of the Pt complex at 200 °C contain nanocrystalline Pt; analysis of the film growth byproducts suggest that the main decomposition pathway involves β-hydrogen elimination and reductive elimination steps, as seen in solution.\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-07-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00186\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00186","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Compounds with Chelating 3-Dimethylamino-1-propyl Ligands as Chemical Vapor Deposition Precursors. Synthesis and Characterization of M[(CH2)3NMe2]2 Complexes of Nickel(II), Palladium(II), and Platinum(II)
We describe the synthesis and characterization of three new square-planar compounds of stoichiometry M[(CH2)3NMe2]2, where M = Ni, Pd, or Pt, each of which contains two chelating 3-dimethylamino-1-propyl ligands. The nickel(II) and palladium(II) compounds decompose above −78 and 0 °C, respectively, but the platinum(II) compound has a thermolysis onset temperature of 130 °C. The Pd and Pt complexes are dynamic in solution: they undergo ring inversion with small free energies of activation of ΔG⧧ = 7.9 ± 0.1 and 8.3 ± 0.1 kcal mol–1, respectively, at 298 K. The Pt complex sublimes at 40 °C and 5 mTorr. In benzene solution, the Pt compound thermolyzes primarily through β-hydrogen elimination; 80 ± 10% of the hydrogen atoms and 75 ± 5% of the carbon atoms from the precursor can be accounted for in the byproducts. The thermolysis of the Pt complex in C6D6 follows first-order kinetics, with an activation free energy ΔG⧧ of 29.9 ± 0.1 kcal mol–1 at 110 °C. Under CVD conditions, thin films grown of the Pt complex at 200 °C contain nanocrystalline Pt; analysis of the film growth byproducts suggest that the main decomposition pathway involves β-hydrogen elimination and reductive elimination steps, as seen in solution.
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.