The Influence of Peripheral Substituent Modification on P(V), Mn(III), and Mn(V)(O) Corrolazines: X-ray Crystallography, Electrochemical and Spectroscopic Properties, and HAT and OAT Reactivities.

Abstract

The influence of remote peripheral substitution on the physicochemical properties and reactivity of phosphorus and manganese corrolazine (Cz) complexes was examined. The substitution of p-MeO for p-t-Bu groups on the eight phenyl substituents of the β-carbon atoms of the Cz ring led to changes in UV-vis transitions and redox potentials for each of the complexes. The oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactivity of the Mn(V)(O) complexes was also influenced by p-MeO substitution. The OAT reactivity of Mn(V)(O)(MeOP8Cz) (MeOP8Cz = octakis(p-methoxyphenyl)corrolazinato(3-)) with triarylphosphine (PAr3) substrates led to second-order rate constants from 10.2(5) to 3.1(2) × 10(4) M(-1) s(-1). These rates of OAT are slower than those seen for Mn(V)(O)(TBP8Cz) (TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)). A Hammett study involving para-substituted PAr3 substrates reveals a Hammett ρ-value for Mn(V)(O)(MeOP8Cz) that is more negative than that observed for Mn(V)(O)(TBP8Cz), consistent with a less electrophilic Mn center. The HAT reactivity of Mn(V)(O)(MeOP8Cz) with C-H substrates was examined and revealed second-order rate constants from 6.8(5) × 10(-5) to 1.70(2) × 10(-1) M(-1) s(-1). The rate constants varied with the C-H bond strength of the substrate. Slightly faster HAT rates with C-H substrates were observed with Mn(V)(O)(MeOP8Cz) compared to Mn(V)(O)(TBP8Cz), indicating that the basicity of the putative [Mn(IV)(O)](-) intermediate likely compensates for the more negative redox potential in the driving force for HAT. In addition, the complete, large-scale synthesis of the para-phenyl-substituted porphyrazines RP8PzH2 (R = p-tert-butylphenyl (TB), p-methoxyphenyl (MeO), and p-isopropylphenyl) and corrolazines RP8CzH3 (TBP8CzH3 and MeOP8CzH3) is presented. The crystal structures of the monoprotonated, metal-free corrolazine [(TBP8CzH3)(H)](+)[BArF](-), P(V)(OMe)2(MeOP8Cz), and Mn(III)(MeOP8Cz)(MeOH) are presented. This work provides the first insights into the influence of electronic substituent effects on the corrolazine periphery.