FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2883969319> ?p ?o ?g. }

• W2883969319 endingPage "2629" @default.
• W2883969319 startingPage "2618" @default.
• W2883969319 abstract "The pincer ligand HN(CH2CH2PPh2)2 (1; PNHP) reacted with [{Ir(μ-X)(cod)}2] (X = Cl, OMe), affording complexes [fac-(PNHP)Ir(cod)]Cl (2) and [fac-(PNP)Ir(cod)] (3), respectively. The X-ray molecular structure of 2 showed that the PNP ligand coordinates in a facial fashion, with the N atom in an axial site and both P atoms coordinated in the equatorial plane. Compound 1 is able to protonate the hydroxo bridges in the complex [{Ir(μ-OH)(coe)2}2] forming the new amido complex [mer-(PNP)Ir(coe)] (4). Complex 4 is an extremely air sensitive compound, as confirmed by the isolation of the oxo complex [mer-(PNP)Ir(η2-O2)] (8) from its interaction with air. Protonation of 4 with HBF4 afforded the corresponding amino complex [mer-(PNHP)Ir(coe)]BF4 (5), whose molecular structure enlightened by X-ray crystallography confirmed the PNP ligand to be coordinated in a meridional fashion. The coe ligand in 4 is tightly bonded to iridium; however, under an atmosphere of ethylene at 60 °C or with acrylonitrile at 70 °C complex 4 exchanges the olefin, affording compounds [mer-(PNP)Ir(η2-C2H4)] (6) and [mer-(PNP)Ir(η2-C2H3CN)] (7), respectively. Interaction of 4 with alkynes depends on the nature of the substrate; therefore, methyl phenylpropiolate reacted with 4, affording the adduct [mer-(PNP)Ir(η2-PhCCC(O)OMe)] (9), while the parent acetylene undergoes a double C–H activation, affording the Ir(III) complex [fac-(PNHP)IrH(C≡CH)2] (10). A DFT theoretical analysis of this transformation supports a metal–ligand cooperation mechanism. The reaction starts by deprotonation of an alkyne moiety by the PNP ligand followed by oxidative addition of the C–H bond to the metal of a second alkyne molecule. Additionally, we have tested complex 4 as a catalyst for the addition of gaseous ammonia to activated unsaturated substrates. A DFT theoretical analysis disclosed the operative mechanism on these organic transformations, which starts with a nucleophilic attack of ammonia to the bound alkyne, hydrogen migration to the metal, and reductive elimination steps." @default.
• W2883969319 created "2018-08-03" @default.
• W2883969319 creator A5001644383 @default.
• W2883969319 creator A5025387429 @default.
• W2883969319 creator A5058063061 @default.
• W2883969319 creator A5075518768 @default.
• W2883969319 creator A5075898630 @default.
• W2883969319 creator A5084501765 @default.
• W2883969319 date "2018-07-27" @default.
• W2883969319 modified "2023-10-18" @default.
• W2883969319 title "Amido Complexes of Iridium with a PNP Pincer Ligand: Reactivity toward Alkynes and Hydroamination Catalysis" @default.
• W2883969319 cites W1542495843 @default.
• W2883969319 cites W1569358764 @default.
• W2883969319 cites W1826118501 @default.
• W2883969319 cites W1843634472 @default.
• W2883969319 cites W1936774904 @default.
• W2883969319 cites W1966559978 @default.
• W2883969319 cites W1969360633 @default.
• W2883969319 cites W1970368062 @default.
• W2883969319 cites W1971425837 @default.
• W2883969319 cites W1972407245 @default.
• W2883969319 cites W1975783169 @default.
• W2883969319 cites W1979704658 @default.
• W2883969319 cites W1982356449 @default.
• W2883969319 cites W1982414593 @default.
• W2883969319 cites W1983715823 @default.
• W2883969319 cites W1987511158 @default.
• W2883969319 cites W1988091937 @default.
• W2883969319 cites W1988897453 @default.
• W2883969319 cites W1990170643 @default.
• W2883969319 cites W1996787420 @default.
• W2883969319 cites W1997909540 @default.
• W2883969319 cites W2000034977 @default.
• W2883969319 cites W2012364998 @default.
• W2883969319 cites W2013720916 @default.
• W2883969319 cites W2014390276 @default.
• W2883969319 cites W2016485004 @default.
• W2883969319 cites W2018653077 @default.
• W2883969319 cites W2022671939 @default.
• W2883969319 cites W2023174370 @default.
• W2883969319 cites W2023271753 @default.
• W2883969319 cites W2023579697 @default.
• W2883969319 cites W2024175762 @default.
• W2883969319 cites W2024953018 @default.
• W2883969319 cites W2026815967 @default.
• W2883969319 cites W2028457395 @default.
• W2883969319 cites W2034465848 @default.
• W2883969319 cites W2037906407 @default.
• W2883969319 cites W2048474386 @default.
• W2883969319 cites W2052685540 @default.
• W2883969319 cites W2056130332 @default.
• W2883969319 cites W2062518453 @default.
• W2883969319 cites W2065836065 @default.
• W2883969319 cites W2073666635 @default.
• W2883969319 cites W2076568297 @default.
• W2883969319 cites W2078981325 @default.
• W2883969319 cites W2081712323 @default.
• W2883969319 cites W2088738831 @default.
• W2883969319 cites W2092157292 @default.
• W2883969319 cites W2097743599 @default.
• W2883969319 cites W2108834225 @default.
• W2883969319 cites W2114419242 @default.
• W2883969319 cites W2114802273 @default.
• W2883969319 cites W2124810596 @default.
• W2883969319 cites W2131350133 @default.
• W2883969319 cites W2131400546 @default.
• W2883969319 cites W2139661138 @default.
• W2883969319 cites W2141921266 @default.
• W2883969319 cites W2142002322 @default.
• W2883969319 cites W2143981217 @default.
• W2883969319 cites W2158945597 @default.
• W2883969319 cites W2161404682 @default.
• W2883969319 cites W2170500592 @default.
• W2883969319 cites W2214754264 @default.
• W2883969319 cites W2288539552 @default.
• W2883969319 cites W2315542586 @default.
• W2883969319 cites W2316125765 @default.
• W2883969319 cites W2316336126 @default.
• W2883969319 cites W2316679889 @default.
• W2883969319 cites W2324462072 @default.
• W2883969319 cites W2330758865 @default.
• W2883969319 cites W2333875011 @default.
• W2883969319 cites W2335169172 @default.
• W2883969319 cites W2335422267 @default.
• W2883969319 cites W2357946441 @default.
• W2883969319 cites W2465355176 @default.
• W2883969319 cites W2517674802 @default.
• W2883969319 cites W2519362337 @default.
• W2883969319 cites W2525130045 @default.
• W2883969319 cites W2535816085 @default.
• W2883969319 cites W2542930749 @default.
• W2883969319 cites W2544810109 @default.
• W2883969319 cites W2553601259 @default.
• W2883969319 cites W2558863965 @default.
• W2883969319 cites W2570786702 @default.
• W2883969319 cites W2580264742 @default.
• W2883969319 cites W2586506508 @default.
• W2883969319 cites W2592220661 @default.

• next