title: 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.
authors.affiliation: Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
authors.forename: Evan E
authors.initials: EE
authors.lastname: Joslin
authors.affiliation: Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
authors.forename: Jan Paulo T
authors.initials: JP
authors.lastname: Zaragoza
authors.affiliation: Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
authors.forename: Regina A
authors.initials: RA
authors.lastname: Baglia
authors.affiliation: Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.affiliation: Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
authors.forename: David P
authors.initials: DP
authors.lastname: Goldberg