Terminal nickel(ii) amide, alkoxide, and thiolate complexes containing amido diphosphine ligands of the type [N(o-C6H4PR2)2]- (R = Ph, (i)Pr, Cy).
A series of nickel(ii) complexes of the type [R-PNP]Ni(ER') ([R-PNP](-) = [N(o-C(6)H(4)PR(2))(2)](-); R = Ph, (i)Pr, Cy; E = NH, O, S; R' = Ph, (t)Bu) featuring unsupported, covalently bound pi-donor ligands have been prepared and characterized. The metathetical reactions of [R-PNP]NiCl (R = Ph, (i)Pr, Cy) with LiNHPh, NaOPh, or NaSPh, respectively, produced the corresponding anilide [R-PNP]Ni(NHPh), phenolate [R-PNP]Ni(OPh), and thiophenolate [R-PNP]Ni(SPh) derivatives. Treatment of [Ph-PNP]NiCl with either LiNH(t)Bu or NaO(t)Bu generated tert-butyl amide [Ph-PNP]Ni(NH(t)Bu) and tert-butoxide [Ph-PNP]Ni(O(t)Bu), respectively. In contrast, attempts to prepare analogous tert-butyl amide and tert-butoxide complexes of [(i)Pr-PNP](-) or [Cy-PNP](-) were not successful. Protonolysis studies of these nickel(ii)-heteroatom complexes revealed the basic reactivity of these pi-donor ligands. The basicity follows the order NH(t)Bu > O(t)Bu > NHPh > OPh > SPh. In addition to solution NMR spectroscopic data for all new compounds, X-ray structures of [(i)Pr-PNP]Ni(NHPh) and [(i)Pr-PNP]Ni(OPh) are presented.
Department of Chemistry and Center for Nanoscience & Nanotechnology, National Sun Yat-sen University, Kaohsiung, 80424, Taiwan. lcliang@mail.nsysu.edu.tw
Lan-Chang
LC
Liang
Pin-Shu
PS
Chien
Pei-Ying
PY
Lee
Jia-Ming
JM
Lin
Yu-Lun
YL
Huang
D000473:Alkanes / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D010720:Phosphines / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D000473:Alkanes; D000577:Amides; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D013438:Sulfhydryl Compounds; D010758:Phosphorus; D009532:Nickel