Conformational Analysis of P,N‐Containing Eight‐Membered Heterocycles and Their Pt/Ni Complexes in Solution

Pt‐ and Pd‐Complexes with Acyclic and Heterocyclic P‐Hydroxyaryl‐Substituted N‐Phosphanylmethyl Amino Acids RP(CH2NHR')2 and (RPCH2NR'CH2)2 – Evaluation of (P^O)M Chelate Formation

“…The structure is in accordance with that inferred from the NMR data and displays, in contrast to 9 as discussed above, the arrangement alternative boat‐boat conformation of the 8‐ring ligand backbone. The different conformations of the free or complex‐bound heterocyclic N 2 P 2 ‐ligands do not differ greatly in energy and may interchange depending on solvent, substituents, or structural environment and temperature . The Pd–Cl, Pd–P, and the bond lengths and most angles of the 8‐membered ring are very similar to the values determined for the [(PhPCH 2 NBzCH 2 ) 2 ]PdCl 2 complex .…”

The Assembly of Unique Hexanuclear Copper(I) Complexes with Effective White Luminescence

“…In our recent works, we demonstrated predominant P,P-chelate − and rather rare P,P-bridge and P,N-chelate ,, coordination modes of 1,5-diaza-3,7-diphosphacyclooctanes containing pyridyl and pyridylethyl substituents on phosphorus atoms in the mono- and dinuclear gold­(I) , and copper­(I) complexes. Reaction of ligands 1 and 2 with a copper­(I) iodide in the 1:3 ligand-to-metal ratio in acetonitrile immediately led to the precipitation of white powders, which were washed, recrystallized from the acetonitrile, and dried over vacuum to give pure white crystalline powders of complexes 3 and 4 in nearly quantitative yield (Scheme ).…”

“…The ligands in this complex have a N,P,­P,N-bridge or μ 4 -coordination mode. The conformation of heterocyclic part of the ligand is a twist-like “chair-boat”, which is rather rare for that type of ligands. ,− The bis-P,P-bridged coordination of two copper­(I) ions forms a 12-membered metallomacrocycle. The cavity of the macrocycle is covered from both sides by the substituents on the one of the nitrogen atoms of each ligand.…”

Pyridyl Containing 1,5-Diaza-3,7-diphosphacyclooctanes as Bridging Ligands for Dinuclear Copper(I) Complexes

“…To assess possible conformational transformations of complexes 3 and 4 in solutions, quantum chemical optimization of various possible conformers of the isolated molecules (see, for example, Figure S9, Supporting Information) was undertaken. As shown elsewhere,, complexes of 1,5‐diaza‐3,7‐diphosphacyclooctanes in solutions typically exist as mixtures of “chair‐chair” (CC) and “chair‐boat” (CB) conformers. Calculated Gibbs free energies of these conformers in vacuo relative to the energetically preferable CB conformers (Δ G ) amount to 4.3 and 4.7 kcal · mol –1 for 3 and 4 , respectively.…”