Bis(benzoxazol‐2‐yl)methanes Hounding NacNac: Varieties and Applications in Main Group Metal Coordination

Abstract

Inspired by the well‐established class of β‐diketiminate or NacNac ligand scaffolds, the systematic building of ligand platforms mimicking its structural features and shielding abilities represents an exciting challenge. One of our focuses in the past decade has been the development of bis(benzheterocyclo)methanes, ‐amines and –phosphanes featuring additional donor‐sites in the ligand backbone as well as increasing steric bulk adjacent to the coordination pocket. This article addresses the variety of obtained ligand scaffolds, highlights some applications in 1, 2 and 13 metal coordination and looks to future developments of even more steric demanding systems to finally complement the famous Dipp‐substituted NacNac system.

Strengths of Acids in Acetonitrile

“…The origin of the compounds published by us earlier, as well as the pK a measurement methods, can be found from the following references: [5,[10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]. The most comprehensive method description is given in ref [5].…”

Benchmarking magnetic and spectroscopic properties on highly stable 3d metal complexes with tuneable bis(benzoxazol-2-yl)methanide ligands

“…18 Furthermore, this system offers an additional oxygen donor site for various coordination motifs. 19 The extension of the aromatic a. M. Sc. Christina M. Legendre, M. Ed.…”

“…Additional substitution along the aromatic system allows steric and geometry control in the third dimension. 19,20 Effective magnetic and steric shielding of the metal atom not only quenches the intermolecular metal-metalcoupling effects but also increases complex stability. 21 Apart from implementation in main group chemistry, 19,22,23 this system has so far neither been employed nor studied for dmetal chemistry.…”

“…19,20 Effective magnetic and steric shielding of the metal atom not only quenches the intermolecular metal-metalcoupling effects but also increases complex stability. 21 Apart from implementation in main group chemistry, 19,22,23 this system has so far neither been employed nor studied for dmetal chemistry. So herein we describe the syntheses and full characterization of the transition metal complexes 1-4.…”

Insight into the Bonding and Aggregation of Alkyllithiums by Experimental Charge Density Studies and Energy Decomposition Analyses

“…These findings substantiate the observation of mixed Li–Cl/Li–CH 3 dimers in solution as presented by Maddaluno et al The increasing electrostatic contribution in smaller aggregates as revealed by our experimental and theoretical analyses now provides additional substantiation to these findings. The addition of halide salts to organometallics to achieve modified reactivity is a synthetic concept of growing interest, even thrivingly shifting the notoriously pyrophoric organolithiums to noninert aqueous conditions. − A detailed knowledge of the interaction of the influence of those mixed organometallics will help to understand their reactivity and will broaden their synthetic application.…”