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

The new hydrazine 5-dibenzo[,]azepin-5-amine (2) reacts with P- and Si-electrophiles deprotonation to afford P(III)-, P(V)-, and TMS-hydrazides 3-8 and with carbonyl electrophiles acid-free condensation to the -substituted hydrazones 9-12 that are potential -alkene ligands. While β-ketohydrazone 9 and α-dihydrazone 10 react with [Mes(Cu)], [Cu(NCCCH)]PF, and FeCl(THF) to afford complexes devoid of alkene interaction, [Cu(OTf)]·CH reacts with the α-keto hydrazone 11 or with , dimethyl-hydrazone 12 to form the neutral dimeric Cu(I) complex 18 with bridging Cu(I)-alkene interactions or the tetrahedral cationic complex 19 in which 12 binds as a bidentate hydrazone-alkene ligand, respectively. The surprising stability of the alkene coordination in complexes 18 and 19 prevents substitutions with, , PPh.

Evolution of a 'privileged' P-alkene ligand: added planar chirality beats BINOL axial chirality in catalytic asymmetric C-C bond formation.

Alkene planar chirality is introduced in the 'privileged' P-alkene phosphoramidite ligand 1. The resulting diastereomeric ligands (p)-5 and (p)-5 form optically pure complexes of Rh(I) and Pd(II), which catalyze conjugate additions of boron C-nucleophiles to enones and allylic alkylations, respectively. In the Rh-catalyzed reaction, the planar chirality of the alkene exerts absolute enantiocontrol over the potent BINOL auxiliary.

Stereochemical Stability of Planar-Chiral Benzazepine Tricyclics: Inversion Energies of P- and S-Alkene Ligands.

Inversion barriers Δ for planar chiral phosphine-alkene and sulfonamide-alkene hybrid ligands based on phenyl-dibenz[]azepine have been determined by density-functional theory calculations. Analysis of the structural and electronic characteristics of the minima and transition states explains the magnitudes of Δ and the geometrical changes during the inversion process. The steric repulsion caused by bulky substituents attached to the azepine nitrogen atom has a pronounced effect on the Δ value, explaining, inter alia, the stereochemical stability of the P- and S-alkene ligands when compared to the fluxional parent compound where X = H.

Trapping of soluble, KCl-stabilized Cu(I) hydrides with CO gives crystalline formates.

Cu(I)-Hydrido complexes supported by dibenzo[]azepinyl -alkene hybrid ligands and stabilized by electrostatic interactions in a Cu-H⋯KCl⋯BR arrangement can be trapped with CO at low temperature to afford Cu(I)-formates. The complexes are isolable with and without a pendant BEt group and show strong Cu-O and weak B-O interactions.

Ir(IV) Sulfoxide-Pincer Complexes by Three-Electron Oxidative Additions of Br and I. Unprecedented Trap-Free Reductive Elimination of I from a formal d Metal.

Oxidative addition of 1.5 equiv of bromine or iodine to a Ir(I) sulfoxide pincer complex affords the corresponding Ir(IV) tris-bromido or tris-iodido complexes, respectively. The unprecedented trap-free reductive elimination of iodine from the Ir(IV)-iodido complex is induced by coordination of ligands or donor solvents.