Putting cyaphide in its place: determining the donor/acceptor properties of the κC-cyaphido ligand

Abstract

The synthesis of group 9 pyridine-diimine complexes M(DippPDI)X and [M(DippPDI)L]+ (M = Co, Rh; DippPDI = 1,1’-(pyridine-2,6-diyl)bis(N-(2,6-diisopropylphenyl)ethan-1-imine; X = CP−, CCH−; L = CO, tBuNC) bearing a series of strong-field...

Metal Influence on Cyaphide‐Azide 1,3‐Dipolar Cycloaddition Reactions: Aromaticity and Activation Strain

“…According to the computed associated stabilization energies, the donation from the cyaphide ligand is comparatively much stronger than the respective backdonation which indicates that the cyaphide ligand is, in these selected complexes, a better σ-donor than πacceptor ligand. [21] The situation for 1-Mg is somehow different because the metal cannot backdonate electron density to the π* molecular orbitals of the cyaphide ligand. As a consequence, besides the expected donation from the lone-pair of the cyaphide to the vacant 3 s atomic orbital of the magnesium (ρ 1 , Figure 1b), there exist two additional weaker donations from the degenerate π molecular orbitals of cyaphide to vacant p atomic orbitals of Scheme 1.…”

An Inorganic Click Reaction for the Synthesis of Interlocked Molecules

“…possessing a bulky and strongly bonded IDipp ligand which prevents dethreading (Scheme 1). [39] The reaction was monitored by 31 P{ 1 H} NMR spectroscopy, with quantitative consumption of Au(IDipp)(CP) after a few hours at room temperature. The formation of 3a was evidenced by the emergence of a new peak in the 31 P{ 1 H} NMR spectrum at 198.6 ppm, alongside the noninterlocked axle 4a which was observed at 199.9 ppm (approx.…”

“…We have recently developed a cyaphide-transfer reagent with Grignard-like reactivity that allows access to a variety of cyaphido metal complexes. [29][30][31] We have also gone on to show that inorganic click reactivity is common to a wide range of metal complexes containing a cyaphide ligand. [32] These cycloaddition reactions proceed rapidly, and in non-polar solvents, to selectively afford the metallo-triazaphospholes in high yields.…”

An Inorganic Click Reaction for the Synthesis of Interlocked Molecules

“…Chemie Zuschriften possessing a bulky and strongly bonded IDipp ligand which prevents dethreading (Scheme 1). [39] The reaction was monitored by 31 P{ 1 H} NMR spectroscopy, with quantitative consumption of Au(IDipp)(CP) after a few hours at room temperature. The formation of 3a was evidenced by the emergence of a new peak in the 31 P{ 1 H} NMR spectrum at 198.6 ppm, alongside the noninterlocked axle 4a which was observed at 199.9 ppm (approx.…”

“…We have recently developed a cyaphide‐transfer reagent with Grignard‐like reactivity that allows access to a variety of cyaphido metal complexes [29–31] . We have also gone on to show that inorganic click reactivity is common to a wide range of metal complexes containing a cyaphide ligand [32] .…”