Trivalent Cations Slow Electron Transfer to Macrocyclic Heterobimetallic Complexes.

Incorporation of secondary redox-inactive cations into heterobimetallic complexes is an attractive strategy for modulation of metal-centered redox chemistry, but quantification of the consequences of incorporating strongly Lewis acidic trivalent cations has received little attention. Here, a family of seven heterobimetallic complexes that pair a redox-active nickel center with La3+, Y3+, Lu3+, Sr2+, Ca2+, K+, and Na+ (in the form of their triflate salts) have been prepared on a heteroditopic ligand platform to understand how chemical behavior varies across the comprehensive series. Structural data from X-ray diffraction analysis demonstrate that the positions adopted by the secondary cations in the crown-ether-like site of the ligand relative to nickel are dependent primarily on the secondary cations' ionic radii and that the triflate counteranions are bound to the cations in all cases. Electrochemical data, in concert with electron paramagnetic resonance studies, show that nickel(II)/nickel(I) redox is modulated by the secondary metals; the heterogeneous electron-transfer rate is diminished for the derivatives incorporating trivalent metals, an effect that is dependent on steric crowding about the nickel metal center and that was quantified here with a topographical free-volume analysis. As related analyses carried out here on previously reported systems bear out similar relationships, we conclude that the placement and identity of both the secondary metal cations and their associated counteranions can afford unique changes in the (electro)chemical behavior of heterobimetallic species.

Remote Oxidative Activation of a [Cp*Rh] Monohydride.

Half-sandwich rhodium monohydrides are often proposed as intermediates in catalysis, but little is known regarding the redox-induced reactivity accessible to these species. Herein, the bis(diphenylphosphino)ferrocene (dppf) ligand has been used to explore the reactivity that can be induced when a [Cp*Rh] monohydride undergoes remote (dppf-centered) oxidation by 1e- . Chemical and electrochemical studies show that one-electron redox chemistry is accessible to Cp*Rh(dppf), including a unique quasi-reversible RhII/I process at -0.96 V vs. ferrocenium/ferrocene (Fc+/0 ). This redox manifold was confirmed by isolation of an uncommon RhII species, [Cp*Rh(dppf)]+ , that was characterized by electron paramagnetic resonance (EPR) spectroscopy. Protonation of Cp*Rh(dppf) with anilinium triflate yielded an isolable and inert monohydride, [Cp*Rh(dppf)H]+ , and this species was found to undergo a quasireversible electrochemical oxidation at +0.41 V vs. Fc+/0 that corresponds to iron-centered oxidation in the dppf backbone. Thermochemical analysis predicts that this dppf-centered oxidation drives a dramatic increase in acidity of the Rh-H moiety by 23 pKa units, a reactivity pattern confirmed by in situ 1 H NMR studies. Taken together, these results show that remote oxidation can effectively induce M-H activation and suggest that ligand-centered redox activity could be an attractive feature for the design of new systems relying on hydride intermediates.