ACS Organic & Inorganic Au最新文献

{"title":"Base Metal Catalyst for Indirect Hydrogenation of CO2","authors":"Jagrit Grover,&nbsp;Suman Maji,&nbsp;Chitrala Teja,&nbsp;Shaeel A. Al Thabaiti*,&nbsp;Mohamed Mokhtar M. Mostafa,&nbsp;Goutam K. Lahiri* and Debabrata Maiti*,&nbsp;","doi":"10.1021/acsorginorgau.3c00023","DOIUrl":"https://doi.org/10.1021/acsorginorgau.3c00023","url":null,"abstract":"<p >We herein report a novel Mn-SNS-based catalyst, which is capable of performing indirect hydrogenation of CO₂ to methanol <i>via</i> formylation. In this domain of CO₂ hydrogenation, pincer ligands have shown a clear predominance. Our catalyst is based on the SNS-type tridentate ligand, which is quite stable and cheap as compared to the pincer type ligands. The catalyst can also be recycled effectively after the formylation reaction without any significant change in efficiency. Various amines including both primary and secondary amines worked well under the protocol to provide the desired formylated product in good yields. The formed formylated amines can also be reduced further at higher pressures of hydrogen. As a whole, we have developed a protocol that involves indirect CO₂ hydrogenation to methanol that proceeds <i>via</i> formylation of amines.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00023","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49768613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Study into the Effects of Countercations on the [P8W48O184]40– Polyoxometalate Wheel","authors":"Daniel Malcolm,&nbsp; and ,&nbsp;Laia Vilà-Nadal*,&nbsp;","doi":"10.1021/acsorginorgau.3c00014","DOIUrl":"https://doi.org/10.1021/acsorginorgau.3c00014","url":null,"abstract":"<p >Porous metal oxide materials have been obtained from a ring-shaped macrocyclic polyoxometalate (POM) structural building unit, [P₈W₄₈O₁₈₄]^40–. This is a tungsten oxide building block with an integrated “pore” of 1 nm in diameter, which, when connected with transition metal linkers, can assemble frameworks across a range of dimensions and which are generally referred to as POMzites. Our investigation proposes to gain a better understanding into the basic chemistry of this POM, specifically local electron densities and locations of countercations within and without the aforementioned pore. Through a rigorous benchmarking process, we discovered that 8 potassium cations, located within the pore, provided us with the most accurate model in terms of mimicking empirical properties to a sufficient degree of accuracy while also requiring a relatively small number of computer cores and hours to successfully complete a calculation. Additionally, we analyzed two other similar POMs from the literature, [As₈W₄₈O₁₈₄]^40– and [Se₈W₄₈O₁₇₆]^32–, in the hopes of determining whether they could be similarly incorporated into a POMzite network; given their close semblance in terms of local electron densities and interaction with potassium cations, we judge these POMs to be theoretically suitable as POMzite building blocks. Finally, we experimented with substituting different cations into the [P₈W₄₈O₁₈₄]^40– pore to observe the effect on pore dimensions and overall reactivity; we observed that the monocationic structures, particularly the Li₈[P₈W₄₈O₁₈₄]^32– framework, yielded the least polarized structures. This correlates with the literature, validating our methodology for determining general POM characteristics and properties moving forward.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49768176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-Density Formation of Ir/MoOx Interface through Hybrid Clustering for Chemoselective Nitrostyrene Hydrogenation","authors":"Shun Hayashi*,&nbsp; and ,&nbsp;Tetsuya Shishido,&nbsp;","doi":"10.1021/acsorginorgau.3c00017","DOIUrl":"https://doi.org/10.1021/acsorginorgau.3c00017","url":null,"abstract":"<p >To form high-density metal/oxide interfacial active sites, we developed a catalyst preparation method based on hybrid clustering. An iridium–molybdenum (Ir–Mo) hybrid clustering catalyst was prepared by using the hybrid cluster [(IrCp*)₄Mo₄O₁₆] (Cp* = η⁵-C₅Me₅) as the precursor. The Ir–Mo hybrid clustering catalyst selectively reduced the nitro group in the hydrogenation of 4-nitrostyrene, whereas the coimpregnated Ir–Mo catalyst reduced both the nitro and vinyl groups nonselectively. The hybrid clustering catalyst also exhibited high selectivity, even at a high Ir loading (5 wt %), in contrast to Ir/MoO₃, which exhibited high selectivity only at low Ir loadings (&lt;0.3 wt %). In situ X-ray absorption spectroscopy analysis revealed that oxygen vacancies were formed at the Ir/MoO_<i>x</i> interface in the presence of H₂. We concluded that a high-density Ir/MoO_<i>x</i> interface contributes to the preferential adsorption of nitro groups on vacant sites, promoting the selective hydrogenation of nitro groups.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00017","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49768652","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of Fluorinated Substituents on the Near-Infrared Phosphorescence of 5d Metallocorroles","authors":"Krister Engedal Johannessen,&nbsp;Martin Amund Langaas Johansen,&nbsp;Rune F. Einrem,&nbsp;Laura J. McCormick McPherson,&nbsp;Abraham B. Alemayehu*,&nbsp;Sergey M. Borisov* and Abhik Ghosh*,&nbsp;","doi":"10.1021/acsorginorgau.3c00016","DOIUrl":"10.1021/acsorginorgau.3c00016","url":null,"abstract":"<p >The influence of fluorinated substituents on the luminescent properties of rhenium-oxo, osmium-nitrido, and gold triarylcorroles was studied via a comparison of four ligands: triphenylcorrole (TPC), tris(<i>p</i>-trifluoromethylphenyl)corrole (T<i>p</i>CF₃PC), tris{3,5-bis(trifluoromethyl)phenyl}corrole (T3,5-CF₃PC), and tris(pentafluorophenyl)corrole (TPFPC). For each metal series examined, fluorinated substituents were found to enhance the luminescent properties, with the phosphorescence quantum yields and triplet decay times increasing in the order TPC &lt; T<i>p</i>CF₃PC &lt; T3,5-CF₃PC &lt; TPFPC. Among the 11 complexes examined, the highest phosphorescence quantum yield, 2.2%, was recorded for Re[TPFPC](O).</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00016","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41180111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-Throughput Determination of Stern–Volmer Quenching Constants for Common Photocatalysts and Quenchers","authors":"Rachel N. Motz,&nbsp;Alexandra C. Sun,&nbsp;Dan Lehnherr and Serge Ruccolo*,&nbsp;","doi":"10.1021/acsorginorgau.3c00019","DOIUrl":"10.1021/acsorginorgau.3c00019","url":null,"abstract":"<p >Mechanistic information on reactions proceeding via photoredox catalysis has enabled rational optimizations of existing reactions and revealed new synthetic pathways. One essential step in any photoredox reaction is catalyst quenching via photoinduced electron transfer or energy transfer with either a substrate, additive, or cocatalyst. Identification of the correct quencher using Stern–Volmer studies is a necessary step for mechanistic understanding; however, such studies are often cumbersome, low throughput and require specialized luminescence instruments. This report describes a high-throughput method to rapidly acquire a series of Stern–Volmer constants, employing readily available fluorescence plate readers and 96-well plates. By leveraging multichannel pipettors or liquid dispensing robots in combination with fast plate readers, the sampling frequency for quenching studies can be improved by several orders of magnitude. This new high-throughput method enabled the rapid collection of 220 quenching constants for a library of 20 common photocatalysts with 11 common quenchers. The extensive Stern–Volmer constant table generated greatly facilitates the systematic comparison between quenchers and can provide guidance to the synthetic community interested in designing and understanding catalytic photoredox reactions.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/4f/02/gg3c00019.PMC10557125.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41156073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nitrogen-Enriched Biguanidine-Functionalized Cobalt Ferrite Nanoparticles as a Heterogeneous Base Catalyst for Knoevenagel Condensation under Solvent-Free Conditions","authors":"Anupam Mishra,&nbsp;Priyanka Yadav and Satish K. Awasthi*,&nbsp;","doi":"10.1021/acsorginorgau.3c00002","DOIUrl":"10.1021/acsorginorgau.3c00002","url":null,"abstract":"<p >Designing efficient, economical heterogeneous catalysts for the Knoevenagel condensation reaction is highly significant owing to the importance of reaction products in industries as well as pharmaceutics. Herein, we have designed and synthesized biguanidine-functionalized basic magnetically retrievable cobalt ferrite nanoparticles (CFNPs) for the synthesis of Knoevenagel condensation products using benzaldehydes and active methylene compounds (malononitrile/ethyl cyanoacetate/cyanoacetamide). Several advanced techniques, such as Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and vibration sample magnetometry (VSM), were utilized to precisely characterize the catalyst. The robust features of the current approach involve outstanding catalytic performance, solvent-free reaction conditions, ease of catalyst retrievability, easy workup procedure, large substrate tolerance, high turnover frequency (TOF) values (up to 486.88 h^–1), values of green chemistry metrics such as E-factor (0.15), reaction mass efficiency (RME) value (87.07%), carbon efficiency (93.4%), and atom economy (AE) value (88.10%) close to their ideal values, and recyclability up to eight runs without a considerable reduction in activity, boosting the appeal of this approach from a commercial and ecological point of view.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/f8/12/gg3c00002.PMC10557060.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41156074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"NO Generation from Nitrite at Zinc(II): Role of Thiol Persulfidation in the Presence of Sulfane Sulfur","authors":"Tuhin Sahana,&nbsp;Adwaith K. Valappil,&nbsp;Anaswar S. P. R. Amma and Subrata Kundu*,&nbsp;","doi":"10.1021/acsorginorgau.3c00004","DOIUrl":"10.1021/acsorginorgau.3c00004","url":null,"abstract":"<p >Nitrite-to-NO transformation is of prime importance due to its relevance in mammalian physiology. Although such a one-electron reductive transformation at various redox-active metal sites (e.g., Cu and Fe) has been illustrated previously, the reaction at the [Zn^II] site in the presence of a sacrificial reductant like thiol has been reported to be sluggish and poorly understood. Reactivity of [(<b>Bn</b>_<b>3</b><b>Tren</b>)Zn^II–ONO](ClO₄) (<b>1</b>), a nitrite-bound model of the tripodal active site of carbonic anhydrase (CA), toward various organic probes, such as 4-<i>tert</i>-butylbenzylthiol (^<i>t</i>BuBnSH), 2,4-di-<i>tert</i>-butylphenol (2,4-DTBP), and 1-fluoro-2,4-dinitrobenzene (F-DNB), reveals that the ONO-moiety in the [Zn^II]–nitrite coordination motif of complex <b>1</b> acts as a mild electrophile. ^<i>t</i>BuBnSH reacts mildly with nitrite at a [Zn^II] site to provide <i>S</i>-nitrosothiol ^<i>t</i>BuBnSNO prior to the release of NO in 10% yield, whereas the phenolic substrate 2,4-DTBP does not yield the analogous <i>O</i>-nitrite compound (ArONO). The presence of sulfane sulfur (S⁰) species such as elemental sulfur (S₈) and organic polysulfides (^<i>t</i>BuBnS_<i>n</i>Bn^<i>t</i>Bu) during the reaction of ^<i>t</i>BuBnSH and [Zn^II]–nitrite (<b>1</b>) assists the nitrite-to-NO conversion to provide NO yields of 65% (for S₈) and 76% (for ^<i>t</i>BuBnS_<i>n</i>Bn^<i>t</i>Bu). High-resolution mass spectrometry (HRMS) analyses on the reaction of [Zn^II]–nitrite (<b>1</b>), ^<i>t</i>BuBnSH, and S₈ depict the formation of zinc(II)-persulfide species [(<b>Bn</b>_<b>3</b><b>Tren</b>)Zn^II–S_<i>n</i>–Bn^<i>t</i>Bu]⁺ (where <i>n</i> = 2, 3, 4, 5, and 6). Trapping of the persulfide species (^<i>t</i>BuBnSS^–) with 1-fluoro-2,4-dinitrobenzene (F-DNB) confirms its intermediacy. The significantly higher nucleophilicity of persulfide species (relative to thiol/thiolate) is proposed to facilitate the reaction with the mildly electrophilic [Zn^II]–nitrite (<b>1</b>) complex. Complementary analyses, including multinuclear NMR, electrospray ionization-MS, UV–vis, and trapping of reactive S-species, provide mechanistic insights into the sulfane sulfur-assisted reactions between thiol and nitrite at the tripodal [Zn^II]-site. These findings suggest the critical influential roles of various reactive sulfur species, such as sulfane sulfur and persulfides, in the nitrite-to-NO conversion.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/92/0c/gg3c00004.PMC10557059.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41160976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Long-Range Kinetic Effects on the Alternating Ring Opening Metathesis of Bicyclo[4.2.0]oct-6-ene-7-carboxamides and Cyclohexene","authors":"Francis O. Boadi,&nbsp; and ,&nbsp;Nicole S. Sampson*,&nbsp;","doi":"10.1021/acsorginorgau.3c00013","DOIUrl":"10.1021/acsorginorgau.3c00013","url":null,"abstract":"<p >We report an investigation of rates of ruthenium-catalyzed alternating ring opening metathesis (AROM) of cyclohexene with two different Ru-cyclohexylidene carbenes derived from bicyclo[4.2.0]oct-6-ene-7-carboxamides (A monomer) that bear different side chains. These monomers are propylbicyclo[4.2.0]oct-6-ene-7-carboxamide and <i>N</i>-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. The amide substitution of these monomers directly affects both the rate of the bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening and the rate of reaction of the resulting carbene with cyclohexene (B monomer). The resulting Ru-cyclohexylidenes underwent reversible ring opening metathesis with cyclohexene. However, the thermodynamic equilibrium disfavored cyclohexene ring opening. Utilization of triphenylphosphine forms a more stable PPh₃ ligated complex, which suppresses the reverse ring closing reaction and allowed direct measurements of the forward rate constants for formation of various A-B and A-B-A′ complexes through carbene-catalyzed ring-opening metathesis and thus gradient polymer structure-determining steps. The relative rate of the propylbicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening is 3-fold faster than that of the <i>N</i>-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. In addition, the rate of cyclohexene ring-opening catalyzed by the propyl bicyclooctene is 1.4 times faster than when catalyzed by the ethoxyethoxy bicyclooctene. Also, the subsequent rates of bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening by propyl-based Ru-hexylidene are 1.6-fold faster than ethoxyethoxy-based Ru-hexylidene. Incorporation of the rate constants into reactivity ratios of bicyclo[4.2.0]amide-cyclohexene provides prediction of copolymerization kinetics and gradient copolymer structures.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/46/7c/gg3c00013.PMC10401671.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9952314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ease of Electrochemical Arsenate Dissolution from FeAsO4 Microparticles during Alkaline Oxygen Evolution Reaction","authors":"Mrinal Kanti Adak,&nbsp;Hirak Kumar Basak and Biswarup Chakraborty*,&nbsp;","doi":"10.1021/acsorginorgau.3c00007","DOIUrl":"https://doi.org/10.1021/acsorginorgau.3c00007","url":null,"abstract":"<p >Transition metal-based ABO₄-type materials have now been paid significant attention due to their excellent electrochemical activity. However, a detailed study to understand the active species and its electro-evolution pathway is not traditionally performed. Herein, FeAsO₄, a bimetallic ABO₄-type oxide, has been prepared solvothermally. In-depth microscopic and spectroscopic studies showed that the as-synthesized cocoon-like FeAsO₄ microparticles consist of several small individual nanocrystals with a mixture of monoclinic and triclinic phases. While depositing FeAsO₄ on three-dimensional nickel foam (NF), it can show oxygen evolution reaction (OER) in a moderate operating potential. During the electrochemical activation of the FeAsO₄/NF anode through cyclic voltammetric (CV) cycles prior to the OER study, an exponential increment in the current density (<i>j</i>) was observed. An ex situ Raman study with the electrode along with field emission scanning electron microscopy imaging showed that the pronounced OER activity with increasing number of CV cycles is associated with a rigorous morphological and chemical change, which is followed by [AsO₄]^3– leaching from FeAsO₄. A chronoamperometric study and subsequent spectro- and microscopic analyses of the isolated sample from the electrode show an amorphous γ-FeO(OH) formation at the constant potential condition. The in situ formation of FeO(OH)_ED (ED indicates electrochemically derived) shows better activity compared to pristine FeAsO₄ and independently prepared FeO(OH). Tafel, impedance spectroscopic study, and determination of electrochemical surface area have inferred that the in situ formed FeO(OH)_ED shows better electro-kinetics and possesses higher surface active sites compared to its parent FeAsO₄. In this study, the electrochemical activity of FeAsO₄ has been correlated with its structural integrity and unravels its electro-activation pathway by characterizing the active species for OER.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49768185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactivity of [(PNP)Mn(CO)2] with Organophosphates","authors":"Brooke N. Livesay,&nbsp;Jurgen G. Schmidt,&nbsp;Robert F. Williams,&nbsp;Brennan S. Billow* and Aaron M. Tondreau*,&nbsp;","doi":"10.1021/acsorginorgau.3c00003","DOIUrl":"https://doi.org/10.1021/acsorginorgau.3c00003","url":null,"abstract":"<p >Organophosphorus nerve agents (OPAs) are a toxic class of synthetic compounds that cause adverse effects with many biological systems. Development of methods for environmental remediation and passivation has been ongoing for years. However, little progress has been made in therapeutic development for exposure victims. Given the postexposure behavior of OPA materials in enzymes such as acetylcholinesterase (AChE), development of electrophilic compounds as therapeutics may be more beneficial than the currently employed nucleophilic countermeasures. In this report, we present our studies with an electrophilic, 16-electron manganese complex (^<i>i</i>PrPNP)Mn(CO)₂ (<b>1</b>) and the nucleophilic hydroxide derivative (^<i>i</i>PrPN^HP)Mn(CO)₂(OH) (<b>2</b>). The reactivity of <b>1</b> with phosphorus acids and the reactivity of <b>2</b> with the P–F bond of diisopropylfluorophosphate (DIPF) were studied. The role of water in both nucleophilic and electrophilic reactivity was investigated with the use of ¹⁷O-labeled water. Promising results arising from reactions of both <b>1</b> and <b>2</b> with organophosphorus substrates are reported.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49768282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}