Bis(diisopropylphosphinomethyl)amine nickel(II) and nickel(0) complexes

• Verfasst von: Kruckenberg, Achim [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Bis(diisopropylphosphinomethyl)amine nickel(II) and nickel(0) complexes
• Titelzusatz: coordination chemistry, reactivity, and catalytic decarbonylative C-H arylation of benzoxazole
• Verf.angabe: Achim Kruckenberg, Hubert Wadepohl, and Lutz H. Gade
• E-Jahr: 2013
• Jahr: September 10, 2013
• Umfang: 18 S.
• Teil: volume:32
• Teil: year:2013
• Teil: number:18
• Teil: month:09
• Teil: pages:5153-5170
• Teil: extent:18
• Fussnoten: Gesehen am 15.06.2021
• Titel Quelle: Enthalten in: Organometallics
• Ort Quelle: Washington, DC : ACS Publ., 1982
• Jahr Quelle: 2013
• Band/Heft Quelle: 32(2013), 18 vom: Sept., Seite 5153-5170
• ISSN Quelle: 1520-6041
• DOI: doi:10.1021/om400711d
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1760456322

Abstract

The facile one-step synthesis of five new bis(diisopropylphosphinomethyl)amine ligands RN(CH2DIP)2 (DIP = diisopropylphosphine, R = Me-, iPr-, PhCH2-, 2-ThCH2-, and 2-FuCH2−) based on the use of the air-stable phosphonium salt [DIP(CH2OH)2]Cl is presented. The phosphonium salt cleanly reacts with primary amines to afford amine-bridged bisphosphine ligands with variable backbone substitution in good yields. These DIP ligands are useful model systems for their chiral bisphospholane analogues. The coordination chemistry of neutral nickel(II) complexes [(RDIP)NiCl2], [(RDIP)Ni(CH3)2], [(iPrDIP)Ni(Cl)CH2Si(CH3)3], and [(RDIP)Ni(CH2Ph)2], as well as coordinatively unsaturated cationic nickel(II) complexes [(RDIP)Ni(THF)CH3]+BArF- and [(RDIP)NiCH2Ph]+BArF-, has been studied by spectroscopic and X-ray diffraction methods. The cationic methyl complexes reacted cleanly with 2-butyne and 1,1-dimethylallene, yielding allylic complexes [(RDIP)Ni(pmcb)]+BArF- and [(RDIP)Ni(tma)]+BArF-, respectively (pmcb: η3-1,2,3,4,4-pentamethylcyclobutenyl; tma: η3-2,3,3-trimethylallyl). Nickel(0) complexes [(BzDIP)Ni(trans-stilbene)] and [(RDIP)Ni(C2H4)] were synthesized in one step from the corresponding dichloro complexes and have been fully characterized and analyzed by X-ray diffraction methods. [(MeDIP)Ni(C2H4)] reacted with phenyl-2-thiophenecarboxylate, yielding [(MeDIP)Ni(OPh)(2-Th)] and [(MeDIP)Ni(CO)2] in a 2:1 ratio. Both complexes were also synthesized via alternative routes. The phenolato-thienyl complex represents an intermediate in the catalytic cycle of a recently reported decarbonylative arylation of azoles. Complexes [(RDIP)Ni(C2H4)] were shown to be active catalysts for this reaction.