title: A terminal nickel(II) anilide complex featuring an unsymmetrically substituted amido pincer ligand: synthesis and reactivity.
abstract: This work describes preparation and reaction chemistry of a terminal nickel(II) anilide complex supported by an unsymmetrically substituted diarylamido diphosphine ligand, [N(o-C(6)H(4)PPh(2))(o-C(6)H(4)P(i)Pr(2))](-) ([Ph-PNP-(i)Pr](-)). Treatment of NiCl(2)(DME) with H[Ph-PNP-(i)Pr] in THF at room temperature produced [Ph-PNP-(i)Pr]NiCl as green crystals in 82% yield. Salt metathesis of [Ph-PNP-(i)Pr]NiCl with LiNHPh(THF) in THF at -35 °C generated cleanly [Ph-PNP-(i)Pr]NiNHPh as a greenish blue solid. The anilide complex deprotonates protic (e.g., PhOH and PhSH) and aprotic (e.g., trimethylsilylacetylene, phenylacetylene, and acetonitrile) acids in benzene at room temperature to give quantitatively [Ph-PNP-(i)Pr]NiX (X = OPh, SPh, C≡CSiMe(3), C≡CPh, CH(2)CN). In addition, [Ph-PNP-(i)Pr]NiNHPh also behaves as a nucleophile to react with acetyl chloride to yield [Ph-PNP-(i)Pr]NiCl and N-phenylacetamide quantitatively. Carbonylation of [Ph-PNP-(i)Pr]NiNHPh with carbon monoxide affords cleanly the carbamoyl derivative [Ph-PNP-(i)Pr]Ni[C(O)NHPh]. The relative bond strengths of Ni-E in [Ph-PNP-(i)Pr]NiEPh (E = NH, O, S, C≡C) are assessed and discussed.
authors.affiliation: Department of Chemistry and Center for Nanoscience & Nanotechnology, National Sun Yat-sen University, Kaohsiung, 80424, Taiwan. lcliang@mail.nsysu.edu.tw
authors.forename: Lan-Chang
authors.initials: LC
authors.lastname: Liang
authors.forename: Chun-Wei
authors.initials: CW
authors.lastname: Li
authors.forename: Pei-Ying
authors.initials: PY
authors.lastname: Lee
authors.forename: Chih-Hsiang
authors.initials: CH
authors.lastname: Chang
authors.forename: Hon Man
authors.initials: HM
authors.lastname: Lee
mesh_terms: D000813:Anilides / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D000813:Anilides; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D009532:Nickel