Ligand Noninnocence in ß-Diketiminate and ß-Diketimine Copper Complexes.

Metal-ligand cooperative systems have a long precedent in catalysis, with the classification depending on the site of substrate bond cleavage and formation and on redox state changes. Recently, our group reported the participation of a ß-diketiminate ligand in chemical bonding to heterocumulenes such as CO2 and CS2 by tricopper complexes, leading to cooperative catalysis. Herein, we report the reactivity of these copper clusters, [Cu3EL]- (E = S, Se; L = tris(ß-diketiminate) cyclophane ligand), toward other electrophiles, viz. alkyl halides and Brønsted acids. We identified a family of ligand-functionalized complexes, Cu3EL (R) (R = primary alkyls), and a series of disubstituted products, Cu3EL (R)2, through single-crystal X-ray diffraction, mass spectrometry, and infrared and UV-visible spectroscopy. As part of mechanistic studies on these alkylation reactions, we evaluated the acid-base reactivity of these complexes and the influence of the backbone substitution on the reduction potential. Implications of these findings for ligand noninnocence and the relevance of the metal core as a cofactor for the ligand's reactivity are discussed.

Metal Site-Specific Electrostatic Field Effects on a Tricopper(I) Cluster Probed by Resonant Diffraction Anomalous Fine Structure (DAFS).

Studies of multinuclear metal complexes are greatly enhanced by resonant diffraction measurements, which probe X-ray absorption profiles of crystallographically independent metal sites within a cluster. In particular, X-ray diffraction anomalous fine structure (DAFS) analysis provides data that can be interpreted akin to site-specific XANES, allowing for differences in metal K-edge resonances to be deconvoluted even for different metal sites within a homometallic system. Despite the prevalence of Cu-containing clusters in biology and energy science, DAFS has yet to be used to analyze multicopper complexes of any type until now. Here, we report an evaluation of trends using a series of strategically chosen Cu(I) and Cu(II) complexes to determine how energy dependencies of anomalous scattering factors are impacted by coordination geometry, ligand shell, cluster nuclearity, and oxidation state. This calibration data is used to analyze a formally tricopper(I) complex that was found by DAFS to be site-differentiated due to the unsymmetrical influence on different Cu sites of the electrostatic field from a proximal K+ cation.