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Orthometalated N-(Benzophenoxazine)-o-aminophenol: Phenolato versus Phenoxyl States.

ABSTRACT: The molecular and electronic structures of the orthometalated ruthenium(III) and osmium(III) complexes of N-(benzophenoxazine)-o-aminophenol (^OXLH₂) that exhibits versatile redox activities are reported. The redox chemistry of ^OXLH₂ is remarkably different from that of N-(aryl)-o-aminophenol (^APLH₂). The study established that ^OXLH₂ is redox noninnocent and is a precursor of a phenoxyl radical. One of the C-H bonds of ^OXLH₂ is activated by ions, and ^OXLH₂ reveals three different redox states as dianionic phenolato (^OXL^2-), monoanionic phenoxyl radical (^OXL^•-), and zwitterionic phenoxium cation (^OXL^±) states. The reaction of ^OXLH₂ with [Ru^II(PPh₃)₃Cl₂] in boiling toluene in air affords an orthometalated ^OXL^2- complex of ruthenium(III), trans-[(^OXL^2-)Ru^III(PPh₃)₂(Cl)] (1), whereas the similar reaction with [Os^II(PPh₃)₃Br₂] yields an orthometalated ^OXL^•- complex, cis-[(^OXL^•-)Os^III(PPh₃)Br₂] (2). 1 and 2 exhibit ligand-based reversible redox waves due to ^OXL^•-/^OXL^2-, ^OXL^±/^OXL^•-, and M^III/M^II couples. The 1 ⁺ ion is a ^OXL^•- complex of ruthenium(III). 2 ^- exhibits temperature-dependent valence tautomerism due to [Os^II(^OXL^•-) ? Os^III(^OXL^2-)] equilibrium. 2 ^2- is a ^OXL^2- complex of osmium(II), while 1 ²⁺ and 2 ⁺ are ^OXL^± complexes of metal(III). 2 is an oxidant and effective catalyst for oxidation of 3,5-di-tert-butylcatechol to the corresponding quinone, and the turnover number is 119.7 h^-1. The UV-vis-NIR absorption spectrum of 1 displays an NIR band at 800 nm due to an intra-ligand-charge-transfer transition, which is absent in 2 incorporating a ^OXL^•- radical. The molecular and electronic structures of 1 and 2 and their oxidized and reduced analogues were confirmed by single-crystal X-ray crystallography, variable-temperature electron paramagnetic resonance spectroscopy, spectroelectrochemical measurements, and density functional theory calculations.

SUBMITTER: Mondal S

PROVIDER: S-EPMC6645054 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Orthometalated N-(Benzophenoxazine)-o-aminophenol: Phenolato versus Phenoxyl States.

Mondal Sandip S Bera Sachinath S Maity Suvendu S Ghosh Prasanta P

ACS omega 20181017 10

The molecular and electronic structures of the orthometalated ruthenium(III) and osmium(III) complexes of N-(benzophenoxazine)-o-aminophenol (OXLH2) that exhibits versatile redox activities are reported. The redox chemistry of OXLH2 is remarkably different from that of N-(aryl)-o-aminophenol (APLH2). The study established that OXLH2 is redox noninnocent and is a precursor of a phen ...[more]

PMID: 31458047

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Project description:INTRODUCTION:Community health centers (CHCs) care for vulnerable patients who use tobacco at higher than national rates. States that expanded Medicaid eligibility under the Affordable Care Act (ACA) provided insurance coverage to tobacco users not previously Medicaid-eligible, thereby potentially increasing their odds of receiving cessation assistance. We examined if tobacco users in Medicaid expansion states had increased quit rates, cessation medications ordered, and greater health care utilization compared to patients in non-expansion states. METHODS:Using electronic health record (EHR) data from 219 CHCs in 10 states that expanded Medicaid as of January 1, 2014, we identified patients aged 19-64 with tobacco use status documented in the EHR within 6 months prior to ACA Medicaid expansion and ?1 visit with tobacco use status assessed within 24 months post-expansion (January 1, 2014 to December 31, 2015). We propensity score matched these patients to tobacco users from 108 CHCs in six non-expansion states (n = 27 670 matched pairs; 55 340 patients). Using a retrospective observational cohort study design, we compared odds of having a quit status, cessation medication ordered, and ?6 visits within the post-expansion period among patients in expansion versus non-expansion states. RESULTS:Patients in expansion states had increased adjusted odds of quitting (adjusted odds ratio [aOR] = 1.35, 95% confidence interval [CI]: 1.28-1.43), having a medication ordered (aOR = 1.53, 95% CI: 1.44-1.62), and having ?6 follow-up visits (aOR = 1.34, 95% CI: 1.28-1.41) compared to patients from non-expansion states. CONCLUSIONS:Increased access to insurance via the ACA Medicaid expansion likely led to increased quit rates within this vulnerable population. IMPLICATIONS:CHCs care for vulnerable patients at higher risk of tobacco use than the general population. Medicaid expansion via the ACA provided insurance coverage to a large number of tobacco users not previously Medicaid-eligible. We found that expanded insurance coverage was associated with increased cessation assistance and higher odds of tobacco cessation. Continued provision of insurance coverage could lead to increased quit rates among high-risk populations, resulting in improvements in population health outcomes and reduced total health care costs.

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Orthometalated N-(Benzophenoxazine)-o-aminophenol: Phenolato versus Phenoxyl States.

Publications

Orthometalated <i>N</i>-(Benzophenoxazine)-<i>o</i>-aminophenol: Phenolato versus Phenoxyl States.

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