Ni(0)-promoted activation of C_sp2–H and C_sp2–O bonds

Abstract

A dinickel(0)-N2 complex, stabilized with a rigid acridane-based PNP pincer ligand, was studied for its ability to activate C(sp2)–H and C(sp2)–O bonds. Stabilized by a Ni-μ-N2-Na+ interaction, it activates C–H...

Comparative study of CO2insertion into pincer supported palladium alkyl and aryl complexes

“…22 Further, the carbon atom bound to palladium (C(1)) is significantly distorted from tetrahedral, with Pd(1)–C(1)–C(2) angles of 127.7(2)° and 123.44(18)° observed for 1-Bn and 1- OMe Bn , respectively. Although this deviation from tetrahedral is typical for Group 10 benzyl complexes, 21 a , c ,23 these are some of the largest angles reported perhaps due to the steric congestion around the palladium.…”

Synthesis and reactivity of a μ-1,2-dinitrogen dinickel(ii) complex with a C–H activated silaamidinate pincer ligand

“…5 Complex 2 features the twisted Ni1–N1–N2–Ni2 array (torsion angle = 35.98°) with the Ni1–N1–N2 and N1–N2–Ni2 bond angles of 169.1 and 171.1°, which are the smallest among the reported nickel dinitrogen molecules (172.6°–178.5°). 3–7 In addition, the N–N vibration 4 b (2101 cm −1 ) of 2 in the IR spectrum (Fig. S12, ESI†) is lower than that of the reported mononuclear Ni( ii ) dinitrogen complexes (2223 and 2220 cm −1 for I and III , respectively).…”

“…2 Following this seminal work, a series of Ni(0) dinitrogen complexes based on phosphine ligands have been reported. 3…”

NMR spectroscopic investigations of transition metal complexes in organometallic and bioinorganic chemistry

“…183 While free organophosphine (PR 3 ) compounds typically exhibit δ P ranging from +23 to À150 ppm, the coordination of phosphines to diamagnetic metal centers significantly alters their δ P values (Figure 4c). 184 Notably, the extent of the change in δ P values (Δδ P ) correlates strongly with the cone angle (θ) of phosphine ligands or M-P distances, indicative of steric effects (Figure 4e). 31 P NMR investigations on a series of cobaloxime complexes, trans-Co III (dimethylglyoxime anion) 2 (PR 3 )(Cl), with various phosphine ligands, demonstrate chemical shift changes along with phosphine coordination.…”