ic9b00256_si_001.pdf (3.72 MB)
Reductive Binding and Ligand-Based Redox Transformations of Nitrosobenzene at a Dinickel(II) Core
journal contribution
posted on 2019-03-25, 00:00 authored by Eleonora Ferretti, Sebastian Dechert, Franc MeyerThe metal-mediated
activation of PhNO represents an important starting point for understanding
the reactivity patterns of nitrosoarenes in biological systems and
catalysis. Here we report that the pyrazole-based dinickel(II) dihydride
complex [KL(NiH)2] (1) reacts with PhNO to
eliminate dihydrogen concomitant with binding of the doubly reduced
substrate in μ-κ(O):κ(N) mode in the bimetallic
pocket of [KLNi2(PhNO)] (2). The addition
of [2,2,2]cryptand leads to the ionic complex [K(crypt)][LNi2(PhNO)] (3). Structural and spectroscopic analyses evidence
that interaction with the Lewis acidic K+ in 2 causes significant elongation and weakening of the substrate’s
N–O bond [dN–O = 1.487(12)
Å in 2 vs 1.374(4) Å in 3]. Complex 2 (or 3) reacts with [FeCp*2][PF6] to give LNi2(PhNO) (4), which is
shown by electron paramagnetic resonance and IR spectroscopies and
density functional theory calculations to feature two low-spin d8 nickel(II) ions and a bridging (PhNO)•– radical anion ligand, with the out-of-plane π*(NO) being the
singly occupied molecular orbital. Cyclic voltammetry and UV–vis
spectroelectrochemical experiments show that 4 and the
anion of 3 can be reversibly interconverted at very low
potential (E1/2 = −1.53 V vs Fc/Fc+). Protonation of 2 leads to the N-phenylhydroxylamine complex [LNi2(ONHPh)] (5) with a long N–O bond of 1.464(2) Å, and titration studies
suggest a pKa of around 23–25 in
tetrahydrofuran. This allows one to derive a bond dissociation energy
of 62–65 kcal mol–1 for the N–H bond
of 5. Accordingly, 5 readily reacts with
the phenoxy radical 2,4,6-tBu3C6H2O• to yield 4. This work demonstrates the reductive binding of PhNO without prior
formation of unstable nickel(I) species and the redox noninnocence
of the PhNO ligand in the less common μ-κ(O):κ(N)
bridging mode. Thermodynamic data for H-atom-abstraction chemistry
at the activated PhNO may be valuable for understanding the reactivity
patterns of the transient but biologically relevant nitroxyl (HNO)
ligand.