The Labile Nature of Air Stable Ni(II)/Ni(0)-phosphine/Olefin Catalysts/Intermediates: EDA-NOCV Analysis.

Metal ions-based inorganic-organic hybrid composites are often reported acting as good to excellent catalysts with various substrate scopes under milder reaction conditions. The active catalyst of a catalytic cycle is sometimes proposed to be a short-lived reactive intermediate species. A three coordinate (L-Me)Ni(II) intermediate species [L-Me=O 2 N donor dianionic ligand] can bind with short-lived carbene-ester ligands to produce four coordinate Ni(II) species which can act as carbene transfer intermediate under suitable reaction conditions for C-H functionalization and/or cyclopropanation reactions. The dissociation of phosphine (PPh 3 ) from the Ni(II) centre of (L-Me)Ni(II)(PPh 3 ) (1 a) and binding of short lived carbene esters (:CR 1 -CO 2 R 2 ; R 1 =H, Ph; R 2 =aliphatic group; 2-4 and other carbenes; 5-10) to Ni(II) rationalize the phenomenon in solution. Air stable Ni(0)-olefin complexes/intermediates (12-18) have recently been shown to mediate a variety of organic transformations. This analysis will further help organic/organometallic chemists to rationalize the design and synthesis of future catalysts for organic transformation. EDA-NOCV calculations have been performed to shed light on the stability and bonding of those species. Additionally, our analysis provides a proper reason why the analogous (L-Me)Pd-PPh 3 complex (1 b) does not dissociate in solution and hence, a similar catalytic product has not been isolated from identical reaction conditions. The stability and the labile nature of Ni(II/0) complexes have been investigated by state-of-the-art EDA-NOCV analyses.