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 6H 4PPh 2)(o-C 6H 4P iPr 2)] - ([Ph-PNP- iPr] -). Treatment of NiCl 2(DME) with H[Ph-PNP- iPr] in THF at room temperature produced [Ph-PNP- iPr]NiCl as green crystals in 82% yield. Salt metathesis of [Ph-PNP- iPr]NiCl with LiNHPh(THF) in THF at -35 °C generated cleanly [Ph-PNP- iPr]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- iPr]NiX (X = OPh, SPh, CCSiMe 3, CCPh, CH 2CN). In addition, [Ph-PNP- iPr]NiNHPh also behaves as a nucleophile to react with acetyl chloride to yield [Ph-PNP- iPr]NiCl and N-phenylacetamide quantitatively. Carbonylation of [Ph-PNP- iPr]NiNHPh with carbon monoxide affords cleanly the carbamoyl derivative [Ph-PNP- iPr]Ni[C(O) NHPh]. The relative bond strengths of Ni-E in [Ph-PNP- iPr]NiEPh (E = NH, O, S, CC) are assessed and discussed.
All Science Journal Classification (ASJC) codes
- Inorganic Chemistry