Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

Abstract

The new mono dibenzo[b,f]-azepinyl substituted P-alkene ligands 7–9, 20, and 21 were used to synthesize monomeric and dimeric Cu(I) complexes by using metal to ligand ratios of 2:1 and 1:1,...

Dibenzoazepine hydrazine is a building block for N-alkene hybrid ligands: exploratory syntheses of complexes of Cu, Fe, and Li

“…nacnac type ligands) have different electronic properties through the second hydrazine nitrogen atom. 5 Some time ago, we and others have introduced 5 H -dibenzo[ b , f ]azepine as a building block for the synthesis of chiral 6 and achiral 7 hemilabile P - and S -alkene hybrid ligands (Chart 1): Ligands I and II feature both point and planar chirality, while the superbulky ligand IV displays a crystallographic Tolman cone angle of 229°. In order to extend the versatility of this building block we envisaged the corresponding hydrazine 5 H -dibenzo[ b , f ]azepin-5-amine ( 2 ) inspired by Grützmacher's 5-amino-5 H -dibenzo[ a , d ]cycloheptene (tropNH 2 ).…”

Trapping of soluble, KCl-stabilized Cu(i) hydrides with CO2 gives crystalline formates

“…Slow addition of KHBEt 3 to a THF solution of the monomeric chlorido complexes 7 or 8 15 at −70 °C affords clear yellow solutions, indicating the formation of hydrido complexes of type 9 and 10 that incorporate KCl (see Scheme 1 and DFT calculations below). These solutions are stable up to −30 °C and rapidly turn brown/black at higher temperatures with metallic copper starting to precipitate (concentrated solutions are markedly more sensitive).…”