On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

Abstract

While β-diketiminate (BDI or 'nacnac') ligands have been widely adopted to stabilize a wide range of metal ions in multiple oxidation states and coordination numbers, in several occurrences these ligands do not behave as spectators and participate in reactivity. Besides unwanted decomposition processes, BDI redox non-innnocence and unusual metal-ligand cooperative activation of substrates yielding attractive reactivity have been reported. This feature article will provide a comprehensive analysis of the various transformations involving BDI ligand platforms in coordination compounds across the periodic table.

N,N′‐Diamidonaphthalene as a Versatile Ligand to Stabilize Mono‐ and Bimetallic Complexes of Group 13

“…1 H, 13 C, and 11 B NMR spectra were run on either a Bruker 300 MHz or Bruker 600 MHz spectrometer using the residual protons of the deuterated solvent for reference. Reaction solvent (anhydrous diethyl ether) was sparged with nitrogen then dried by passage through column of activated alumina using an apparatus purchased from Anhydrous Engineering.…”

“…[21] Semi-empirical absorption corrections based on equivalent reflections were applied. The hydrogen atoms were placed in idealized positions, except for H (1) . The structures were solved by direct methods and refined with full-matrix least-squares procedures based on F 2 , using SHELXL [23] and WinGX.…”

“…[1][2][3][4] As supporting ligands, -diketiminates exhibit strong and diverse binding modes combined with adjustable steric demands through variation of the NR substituents and these features have promoted their application in group 13 and across the periodic Table These observations provided an impetus for our efforts to design and implement ligands that are reminiscent of the -diketiminate scaffold in both geometry and frontier orbital topology and this target has led us to investigate the application of the dianions, N,N′disubstituted-1,8-diamidonaphthalene ("R 2 DAN 2-") as ligands in group 13 chemistry. They can be exploited from both fundamental and applied perspectives and have been employed for their reactivity and as building blocks in synthesis.…”

“…They can be exploited from both fundamental and applied perspectives and have been employed for their reactivity and as building blocks in synthesis. With R = Ph, a monometallic aluminum complex, MeAl(OEt 2 )- [1, 2 C 10 H 6 ] (6), was isolated as a diethylether adduct. For example, the application of -diketiminate ligands has vitalized the synthetic chemistry of group 13 elements.…”

Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

“…Only in certain exceptions, [11] there is evidencef or irreversible degradation of the b-diketiminato ligand. [12] The use of pendant amino groups on thesem ultidentate ligandss tems from the fact that scandium imides [3] can be generated or trapped with donor ligands such as pyridine or pyridine derivatives (e.g. DMAP) as exemplified by the work of Mindiola, [13] Cui, [14] Piers, [15] and more recently,Mountford.…”