Pub Date : 2020-02-23DOI: 10.1080/02603594.2020.1726328
Notashia N. Baughman, Brian V. Popp
ABSTRACT In this comment, insights gained from density functional theory into the mechanism by which the Cu(I)-catalyzed boracarboxylation of vinyl arenes occurs with specific focus on the CO2 insertion step are presented. Preliminary calculations indicated a potential non-covalent interaction between boron and CO2 in the carboxylation transition state, implicating cooperative CO2 activation. A study of boron Lewis acidity was conducted through substitution of sp2 mono-boron substituents. An inverse correlation between boron valence deficiency (BVD) and the enthalpic barrier of CO2 insertion into the β-borylbenzyl-Cu(I) bond was revealed, supporting Lewis acid/base cooperativity between boron and the proximal oxygen of CO2 at the carboxylation insertion transition state. These findings suggest that future methodology development should consider strategic incorporation of similar Lewis acidic functionality to facilitate carboxylation of challenging substrates. Graphical abstract
在这篇评论中，从密度泛函理论中获得了对Cu(I)催化乙烯基芳烃硼羧化发生机理的见解，并特别关注了CO2插入步骤。初步计算表明，在羧基化过渡态，硼和CO2之间可能存在非共价相互作用，这意味着协同CO2活化。采用sp2单硼取代基对硼的路易斯酸性进行了研究。硼价缺位(BVD)与CO2插入β-硼基苄基- cu (I)键的焓势之间呈负相关，支持了在羧基化插入过渡态硼与CO2近端氧之间的Lewis酸/碱协同作用。这些发现表明，未来的方法发展应该考虑战略性地结合类似的刘易斯酸性功能，以促进具有挑战性的底物的羧基化。图形抽象
{"title":"Evidence of Boron Assistance for CO2 Activation during Copper-Catalyzed Boracarboxylation of Vinyl Arenes: A Synthetic Model for Cooperative Fixation of CO2","authors":"Notashia N. Baughman, Brian V. Popp","doi":"10.1080/02603594.2020.1726328","DOIUrl":"https://doi.org/10.1080/02603594.2020.1726328","url":null,"abstract":"ABSTRACT In this comment, insights gained from density functional theory into the mechanism by which the Cu(I)-catalyzed boracarboxylation of vinyl arenes occurs with specific focus on the CO2 insertion step are presented. Preliminary calculations indicated a potential non-covalent interaction between boron and CO2 in the carboxylation transition state, implicating cooperative CO2 activation. A study of boron Lewis acidity was conducted through substitution of sp2 mono-boron substituents. An inverse correlation between boron valence deficiency (BVD) and the enthalpic barrier of CO2 insertion into the β-borylbenzyl-Cu(I) bond was revealed, supporting Lewis acid/base cooperativity between boron and the proximal oxygen of CO2 at the carboxylation insertion transition state. These findings suggest that future methodology development should consider strategic incorporation of similar Lewis acidic functionality to facilitate carboxylation of challenging substrates. Graphical abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"7 1","pages":"159 - 175"},"PeriodicalIF":5.4,"publicationDate":"2020-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74346759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-01-31DOI: 10.1080/02603594.2020.1718120
O. Mikhailov, D. Chachkov
ABSTRACT Based on the quantum-chemical calculation using the Density Functional Theory (DFT) method, the existence possibility of zinc heteroligand complexes with porphyrazine and its analogs – trans-di[benzo]porphyrazine or phthalocyanine and oxo ligands with an oxidation state of IV which is unknown for this element, was shown. The data on the structural parameters and multiplicity of the ground state of these complexes were presented. Graphical Abstract Comments on Inorganic Chemistry Volume ……., Issue ……., Pages ………. (2020). About of Possibility of Existence of Zn(IV) Oxidation State in Heteroligand Complexes with Porphyrazine, trans-Di[benzo]porphyrazine, Phthalocyanine and Oxo Ligands: Quantum-Chemical Review. Oleg V. Mikhailov, Denis V. Chachkov
{"title":"About of Possibility of Existence of Zn(IV) Oxidation State in Heteroligand Complexes with Porphyrazine, trans-Di[benzo]porphyrazine, Phthalocyanine, and Oxo Ligands: Quantum-Chemical Review","authors":"O. Mikhailov, D. Chachkov","doi":"10.1080/02603594.2020.1718120","DOIUrl":"https://doi.org/10.1080/02603594.2020.1718120","url":null,"abstract":"ABSTRACT Based on the quantum-chemical calculation using the Density Functional Theory (DFT) method, the existence possibility of zinc heteroligand complexes with porphyrazine and its analogs – trans-di[benzo]porphyrazine or phthalocyanine and oxo ligands with an oxidation state of IV which is unknown for this element, was shown. The data on the structural parameters and multiplicity of the ground state of these complexes were presented. Graphical Abstract Comments on Inorganic Chemistry Volume ……., Issue ……., Pages ………. (2020). About of Possibility of Existence of Zn(IV) Oxidation State in Heteroligand Complexes with Porphyrazine, trans-Di[benzo]porphyrazine, Phthalocyanine and Oxo Ligands: Quantum-Chemical Review. Oleg V. Mikhailov, Denis V. Chachkov","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"202 1","pages":"107 - 115"},"PeriodicalIF":5.4,"publicationDate":"2020-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74886076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-01-02DOI: 10.1080/02603594.2019.1701448
M. Omary, John J. Determan, Chammi S. Palehepitiya Gamage, P. Sinha, Shan Li, Monika R. Patterson, Vladimir N. Nestero, A. Wilson, H. V. Rasika Dias
ABSTRACT This paper provides a 4th manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry. (For the 1st, 2nd and 3rd manifestations, see: a) Otten, B. M.; Melancon, K. M.; Omary, M. A. “All That Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers – A Tribute to Al Cotton on the 10th Anniversary of His Passing,” Comments Inorg. Chem. 2018, 38, 1–35; b) Yaseen, W. K.; Sanders, S. F.; Almotawa, R. M.; Otten, B. M.; Bhat, S.; Alamo, D. C.; Marpu, S. B.; Golden, T. D.; Omary, M. A. “Are Metal Complexes “Organic”, “Inorganic”, “Organometallic”, or “Metal-Organic” Materials? A Case Study for the Use of Trinuclear Coinage Metal Complexes as “Metal-Organic Coatings” for Corrosion Suppression on Aluminum Substrates”, Comments Inorg. Chem. 2019, 39, 1–26; and c) Smith, J. B.; Otten, B. M.; Derry, P. J.; Browning, C.; Bodenstedt, K. W.; Sandridge, J. H.; Satumtira, N. T.; Zilaie, M.; Payne, J.; Nuti, R.; Omary, M. A.; Smucker, B. W. “Luminescent, Redox-Active (Dithiolato)Bis(Imine)Platinum(II) Divergent Complexes with Exchangeable Imine Ligands: An Experimental/Computational Study versus Their (Diimine)(Dithiolato)Platinum(II) Convergent Congeners”, Comments Inorg. Chem. 2019, 39, 188–215.) Herein, the dinuclear complexes {Cu[3,5-(CF3)2Pz](µ-dppm)}2 and {Cu[3,5-(CF3)2Pz](µ-dppm)}2•3THF were studied structurally, spectroscopically and via density functional theory (DFT). They were synthesized by reacting bis(diphenylphosphino)methane (dppm) with the cyclic trinuclear complex {μ-[3,5-(CF3)2Pz]Cu}3 to effect nuclearity reduction. Two forms of crystalline solids, {Cu[3,5-(CF3)2Pz](µ-dppm)}2 and {Cu[3,5-(CF3)2Pz](µ-dppm)}2•3THF have been obtained using different recrystallization conditions. The {Cu[3,5-(CF3)2Pz](µ-dppm)}2 complex was found through DFT computations to undergo a distortion from a Y-shaped coordination sphere in the S0 ground state toward a T-shape in the T1 photoexcited, lowest-lying, phosphorescent state. The distortion also causes the copper-copper bond length to contract and form an excimer bond (dCu-Cu = 2.577 Å). Experimentally, the presence of THF in the crystal was found to cause a blue shift, effecting a change in emission color from teal to blue to the naked eye, with a near-unity quantum yields (93%), rendering the latter solid suitable for inorganic LED applications but not OLEDs, as thin films exhibit a reduced quantum yield. Crystallographic evidence suggests that THF leads to a more compact lattice that makes the complexes more rigid and thus hinder the excited state distortions vs unsolvated crystals. Greater distortion leads to a lower energy radiative emission and thus a red shift in the emission color. Films wer
{"title":"Is a High Photoluminescence Quantum Yield Good Enough for OLEDs? Can Luminescence Rigidochromism Be Manifest in the Solid State? an Optoelectronic Device Screening Case Study for Diphosphine/Pyrazolate Copper(I) Complexes","authors":"M. Omary, John J. Determan, Chammi S. Palehepitiya Gamage, P. Sinha, Shan Li, Monika R. Patterson, Vladimir N. Nestero, A. Wilson, H. V. Rasika Dias","doi":"10.1080/02603594.2019.1701448","DOIUrl":"https://doi.org/10.1080/02603594.2019.1701448","url":null,"abstract":"ABSTRACT This paper provides a 4th manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry. (For the 1st, 2nd and 3rd manifestations, see: a) Otten, B. M.; Melancon, K. M.; Omary, M. A. “All That Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers – A Tribute to Al Cotton on the 10th Anniversary of His Passing,” Comments Inorg. Chem. 2018, 38, 1–35; b) Yaseen, W. K.; Sanders, S. F.; Almotawa, R. M.; Otten, B. M.; Bhat, S.; Alamo, D. C.; Marpu, S. B.; Golden, T. D.; Omary, M. A. “Are Metal Complexes “Organic”, “Inorganic”, “Organometallic”, or “Metal-Organic” Materials? A Case Study for the Use of Trinuclear Coinage Metal Complexes as “Metal-Organic Coatings” for Corrosion Suppression on Aluminum Substrates”, Comments Inorg. Chem. 2019, 39, 1–26; and c) Smith, J. B.; Otten, B. M.; Derry, P. J.; Browning, C.; Bodenstedt, K. W.; Sandridge, J. H.; Satumtira, N. T.; Zilaie, M.; Payne, J.; Nuti, R.; Omary, M. A.; Smucker, B. W. “Luminescent, Redox-Active (Dithiolato)Bis(Imine)Platinum(II) Divergent Complexes with Exchangeable Imine Ligands: An Experimental/Computational Study versus Their (Diimine)(Dithiolato)Platinum(II) Convergent Congeners”, Comments Inorg. Chem. 2019, 39, 188–215.) Herein, the dinuclear complexes {Cu[3,5-(CF3)2Pz](µ-dppm)}2 and {Cu[3,5-(CF3)2Pz](µ-dppm)}2•3THF were studied structurally, spectroscopically and via density functional theory (DFT). They were synthesized by reacting bis(diphenylphosphino)methane (dppm) with the cyclic trinuclear complex {μ-[3,5-(CF3)2Pz]Cu}3 to effect nuclearity reduction. Two forms of crystalline solids, {Cu[3,5-(CF3)2Pz](µ-dppm)}2 and {Cu[3,5-(CF3)2Pz](µ-dppm)}2•3THF have been obtained using different recrystallization conditions. The {Cu[3,5-(CF3)2Pz](µ-dppm)}2 complex was found through DFT computations to undergo a distortion from a Y-shaped coordination sphere in the S0 ground state toward a T-shape in the T1 photoexcited, lowest-lying, phosphorescent state. The distortion also causes the copper-copper bond length to contract and form an excimer bond (dCu-Cu = 2.577 Å). Experimentally, the presence of THF in the crystal was found to cause a blue shift, effecting a change in emission color from teal to blue to the naked eye, with a near-unity quantum yields (93%), rendering the latter solid suitable for inorganic LED applications but not OLEDs, as thin films exhibit a reduced quantum yield. Crystallographic evidence suggests that THF leads to a more compact lattice that makes the complexes more rigid and thus hinder the excited state distortions vs unsolvated crystals. Greater distortion leads to a lower energy radiative emission and thus a red shift in the emission color. Films wer","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"29 1","pages":"1 - 24"},"PeriodicalIF":5.4,"publicationDate":"2020-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76442468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-01-02DOI: 10.1080/02603594.2019.1701447
Matthew F. Cain
ABSTRACT While initially laboratory curiosities, the chemistry of phospholes evolved as a better understanding of their structure, reactivity, and electronic properties was established. With their potential as building blocks for new electronic materials emerging, researchers started to investigate phospholes that maximized π-conjugation. Subsequently, numerous heteroatom-substituted derivatives with a σ2,λ3 P-center were reported, but one particular analog, 1,2-(benz)azaphospholes was noticeably absent, likely due to unusual/impractical synthetic methods. A serendipitous synthetic discovery in 2016 provided straightforward access to these highly aromatic 6π-electron (10π if the fused benzene ring is included) heterocycles. Early reactivity studies have shown that the functionalized products of these rare heterocycles have unusual structures and may find application as catalysts for hydrofunctionalization, as new types of transmetallation agents, or as reactive centers for strong bond activation. GRAPHICAL ABSTRACT
{"title":"1,2-(Benz)Azaphospholes: A Slow Beginning to a Bright Future","authors":"Matthew F. Cain","doi":"10.1080/02603594.2019.1701447","DOIUrl":"https://doi.org/10.1080/02603594.2019.1701447","url":null,"abstract":"ABSTRACT While initially laboratory curiosities, the chemistry of phospholes evolved as a better understanding of their structure, reactivity, and electronic properties was established. With their potential as building blocks for new electronic materials emerging, researchers started to investigate phospholes that maximized π-conjugation. Subsequently, numerous heteroatom-substituted derivatives with a σ2,λ3 P-center were reported, but one particular analog, 1,2-(benz)azaphospholes was noticeably absent, likely due to unusual/impractical synthetic methods. A serendipitous synthetic discovery in 2016 provided straightforward access to these highly aromatic 6π-electron (10π if the fused benzene ring is included) heterocycles. Early reactivity studies have shown that the functionalized products of these rare heterocycles have unusual structures and may find application as catalysts for hydrofunctionalization, as new types of transmetallation agents, or as reactive centers for strong bond activation. GRAPHICAL ABSTRACT","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"35 1","pages":"25 - 51"},"PeriodicalIF":5.4,"publicationDate":"2020-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86857300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-11-02DOI: 10.1080/02603594.2019.1666371
R. Galassi, Manal A. Rawashdeh-Omary, H. V. Rasika Dias, M. Omary
Trinuclear coinage metal metallacycles are obtained when two-coordinate metals are bonded to C, N or N, N anionic ligands of the proper symmetry to form cycles where metals alternate with bridging ligands. Cyclotrimers often exhibit semiplanar structures and mostly columnar or finite stacking in the solid state by means of metallophilic interactions. They show some peculiar properties with an impact on many different fields such as supramolecular architectures, luminescence, molecular recognition, host-guest chemistry, and acid-base chemistry. The comprehensive evaluation of the data shows that, depending on the nature of the central metal and bridging ligand, there is a fine balance of the energy involved in the inter-trimer bond cleavages and the energy gained from the formation of new intermolecular electrostatic interactions, proceeding occasionally to the chemical extreme of redox processes. In this review, a number of important developments are highlighted and systematically analyzed along with structural and computational data and chemical properties to rationalize and build a unifying leitmotif for this chemistry; the focus is made on the authors’ contributions in these areas. Graphical Abstract
{"title":"Homoleptic Cyclic Trinuclear d10 Complexes: from Self-Association via Metallophilic and Excimeric Bonding to the Breakage Thereof via Oxidative Addition, Dative Bonding, Quadrupolar, and Heterometal Bonding Interactions","authors":"R. Galassi, Manal A. Rawashdeh-Omary, H. V. Rasika Dias, M. Omary","doi":"10.1080/02603594.2019.1666371","DOIUrl":"https://doi.org/10.1080/02603594.2019.1666371","url":null,"abstract":"Trinuclear coinage metal metallacycles are obtained when two-coordinate metals are bonded to C, N or N, N anionic ligands of the proper symmetry to form cycles where metals alternate with bridging ligands. Cyclotrimers often exhibit semiplanar structures and mostly columnar or finite stacking in the solid state by means of metallophilic interactions. They show some peculiar properties with an impact on many different fields such as supramolecular architectures, luminescence, molecular recognition, host-guest chemistry, and acid-base chemistry. The comprehensive evaluation of the data shows that, depending on the nature of the central metal and bridging ligand, there is a fine balance of the energy involved in the inter-trimer bond cleavages and the energy gained from the formation of new intermolecular electrostatic interactions, proceeding occasionally to the chemical extreme of redox processes. In this review, a number of important developments are highlighted and systematically analyzed along with structural and computational data and chemical properties to rationalize and build a unifying leitmotif for this chemistry; the focus is made on the authors’ contributions in these areas. Graphical Abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"23 1","pages":"287 - 348"},"PeriodicalIF":5.4,"publicationDate":"2019-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83879840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-08-05DOI: 10.1080/02603594.2019.1643331
I. V. Lisnevskaya, V. Butova, Mikhail I. Perebeinos, K. V. Myagkaya, A. Letovaltsev, V. Shapovalov, H. Zahran, I. Yahia, A. Soldatov
BiMnO3 exhibit multiferroic properties, which attract much attention due to numerous potential applications. The most well-investigated and traditional techniques for synthesizing this material include high-pressure and high-temperature treatment. In this way, soft chemistry synthesis of BiMnO3 is desirable. Even though the formation of BiMnO3 at ambient pressure is not possible according to the phase diagram, many scientific groups are focused on solving this problem. In the present work, we have tested four soft chemistry routes, namely hydrothermal route, two gel methods, and coprecipitation for synthesizing BiMnO3 from Cl– and NO3–-containing solutions at ambient pressure in the temperature range of 200–800°C, and none resulted in the formation of BiMnO3. The experiment showed that under hydrothermal conditions manganese and bismuth oxides remain unreacted, and the other tested methods produce Bi2Mn4O10 and Bi12MnO20 instead. The formation of Bi2Mn4O10 and Bi12MnO20 from Cl–-containing solutions occurs with BiOCl being formed as an intermediate phase. Graphical Abstract
{"title":"On the Possibility of Synthesizing Bimno3 at Ambient Pressure Using Low-Temperature Methods","authors":"I. V. Lisnevskaya, V. Butova, Mikhail I. Perebeinos, K. V. Myagkaya, A. Letovaltsev, V. Shapovalov, H. Zahran, I. Yahia, A. Soldatov","doi":"10.1080/02603594.2019.1643331","DOIUrl":"https://doi.org/10.1080/02603594.2019.1643331","url":null,"abstract":"BiMnO3 exhibit multiferroic properties, which attract much attention due to numerous potential applications. The most well-investigated and traditional techniques for synthesizing this material include high-pressure and high-temperature treatment. In this way, soft chemistry synthesis of BiMnO3 is desirable. Even though the formation of BiMnO3 at ambient pressure is not possible according to the phase diagram, many scientific groups are focused on solving this problem. In the present work, we have tested four soft chemistry routes, namely hydrothermal route, two gel methods, and coprecipitation for synthesizing BiMnO3 from Cl– and NO3–-containing solutions at ambient pressure in the temperature range of 200–800°C, and none resulted in the formation of BiMnO3. The experiment showed that under hydrothermal conditions manganese and bismuth oxides remain unreacted, and the other tested methods produce Bi2Mn4O10 and Bi12MnO20 instead. The formation of Bi2Mn4O10 and Bi12MnO20 from Cl–-containing solutions occurs with BiOCl being formed as an intermediate phase. Graphical Abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"13 1","pages":"270 - 286"},"PeriodicalIF":5.4,"publicationDate":"2019-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78709287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-06-24DOI: 10.1080/02603594.2019.1628025
Ying-shu Liu, K. Leung, Samuel E. Michaud, Taylor L. Soucy, Charles C. L. McCrory
The selective electrochemical reduction of CO2 to value-added products is a useful strategy for the local storage of intermittent energy sources as chemical fuels and the recycling of industrial CO2 waste into industrial feedstocks. This review highlights some of the recent research focused specifically on modulating substrate delivery and local catalyst environment to enhance reaction and product selectivity in the CO2 reduction reaction by both solid-state materials and discrete molecular systems. We discuss recent studies that focus on (1) using nanostructured and mesoporous solid-state electrocatalysts to modulate local pH and CO2 concentrations near active sites, (2) coating electrocatalysts with porous overlayers to directly control substrate delivery to the electrocatalyst surface, and (3) using polymer encapsulation to modify the coordination environment surrounding molecular electrocatalysts to enhance activity and selectivity for CO2 reduction. We believe that increased research in controlling substrate delivery to enhance reaction and product selectivity for the CO2 reduction reaction is a promising strategy for designing new electrocatalytic systems for the selective and efficient conversion of CO2 to value-added products. Graphical abstract
{"title":"Controlled Substrate Transport to Electrocatalyst Active Sites for Enhanced Selectivity in the Carbon Dioxide Reduction Reaction","authors":"Ying-shu Liu, K. Leung, Samuel E. Michaud, Taylor L. Soucy, Charles C. L. McCrory","doi":"10.1080/02603594.2019.1628025","DOIUrl":"https://doi.org/10.1080/02603594.2019.1628025","url":null,"abstract":"The selective electrochemical reduction of CO2 to value-added products is a useful strategy for the local storage of intermittent energy sources as chemical fuels and the recycling of industrial CO2 waste into industrial feedstocks. This review highlights some of the recent research focused specifically on modulating substrate delivery and local catalyst environment to enhance reaction and product selectivity in the CO2 reduction reaction by both solid-state materials and discrete molecular systems. We discuss recent studies that focus on (1) using nanostructured and mesoporous solid-state electrocatalysts to modulate local pH and CO2 concentrations near active sites, (2) coating electrocatalysts with porous overlayers to directly control substrate delivery to the electrocatalyst surface, and (3) using polymer encapsulation to modify the coordination environment surrounding molecular electrocatalysts to enhance activity and selectivity for CO2 reduction. We believe that increased research in controlling substrate delivery to enhance reaction and product selectivity for the CO2 reduction reaction is a promising strategy for designing new electrocatalytic systems for the selective and efficient conversion of CO2 to value-added products. Graphical abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"35 1","pages":"242 - 269"},"PeriodicalIF":5.4,"publicationDate":"2019-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77686017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-05-23DOI: 10.1080/02603594.2019.1608967
Jordi Cirera, E. Ruiz
A survey of different computational approaches to compute thermochemical properties and, in particular, transition temperatures (T1/2) in spin-crossover (SCO) systems are presented. Asides from the possibility of computing accurate values, this work centers its efforts in the use of computational tools to explain trends in different families of SCO molecules. Understanding the impact that chemical modifications (both electronic and steric) have over the ligand-field around the metal center is key in rationalizing the observed trends in T1/2. By using concepts from molecular orbital theory combined with the results from the calculations, a simple yet, accurate depiction of the shift in T1/2 can be outlined. Therefore, the presented results allow for a rational design of new SCO systems with tailored properties.
{"title":"Computational Modeling of Transition Temperatures in Spin-Crossover Systems","authors":"Jordi Cirera, E. Ruiz","doi":"10.1080/02603594.2019.1608967","DOIUrl":"https://doi.org/10.1080/02603594.2019.1608967","url":null,"abstract":"A survey of different computational approaches to compute thermochemical properties and, in particular, transition temperatures (T1/2) in spin-crossover (SCO) systems are presented. Asides from the possibility of computing accurate values, this work centers its efforts in the use of computational tools to explain trends in different families of SCO molecules. Understanding the impact that chemical modifications (both electronic and steric) have over the ligand-field around the metal center is key in rationalizing the observed trends in T1/2. By using concepts from molecular orbital theory combined with the results from the calculations, a simple yet, accurate depiction of the shift in T1/2 can be outlined. Therefore, the presented results allow for a rational design of new SCO systems with tailored properties.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"111 1","pages":"216 - 241"},"PeriodicalIF":5.4,"publicationDate":"2019-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87910597","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2019-04-22DOI: 10.1080/02603594.2019.1594204
R. Mohapatra, P. Das, M. Pradhan, M. El-ajaily, D. Das, H. F. Salem, U. Mahanta, Gouranga Badhei, P. Parhi, A. Maihub, M. E-Zahan
Ureas and thioureas, otherwise known as carbamides and thiocarbamides, respectively, are rich sources of nitrogen. Urea has a wide range of applications in agriculture, the chemical industry, and automobile systems, and is an important chemical in medical uses. Thiourea, an organosulfur compound, has long been known as an important reagent in organic synthesis, and has been employed in textile processing, used as a source of sulphides, and acts as a precursor in the synthesis of several heterocyclic compounds. The exceptional ligating properties of these compounds enable them to form a large number of complex compounds with transition metals, a vast majority of which find abundant applications in potential areas. This has stimulated researchers to explore novel applications of the synthesized ligands and the metal complexes thereof. This review presents a report of the studies on the biological activities, sensor properties, opical nonlinear properties, corrosion inhibitior potential, and catalytic activities of these compounds and their metal complexes. Graphical abstract
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Pub Date : 2019-04-08DOI: 10.1080/02603594.2019.1594205
Jacob B. Smith, Brooke M. Otten, Paul J. Derry, C. Browning, Kurt Bodenstedt, Jessie H. Sandridge, Nisa T. Satumtira, Mina Zilaie, Jon Payne, R. Nuti, M. Omary, B. Smucker
This article provides a third manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the journal’s identity as a niche for “critical discussion” of contemporary literature in inorganic chemistry. (For the first and second manifestations, see: (1) Otten, B. M.; Melancon, K. M.; Omary, M. A. “All that Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers: A Tribute to Al Cotton on the 10th Anniversary of His Passing,” Comments Inorg. Chem. 2018, 38, 1–35; (2) Yaseen, W. K.; Sanders, S. F.; Almotawa, R. M.; Otten, B. M.; Bhat, S.; Alamo, D. C.; Marpu, S. B.; Golden, T. D.; Omary, M. A. “Are Metal Complexes ‘Organic’, ‘Inorganic’, ‘Organometallic’, or ‘Metal-Organic’ Materials? A Case Study for the Use of Trinuclear Coinage Metal Complexes as ‘Metal-Organic Coatings’ for Corrosion Suppression on Aluminum Substrates,” Comments Inorg. Chem. 2019, 39, 1–26.) Herein, we contrast the electronic structure of two categories of Pt(II) complexes with mixed imine/thiolato ligands: a new class of [Pt(N^N)2(S^S)] bis(κ1-diimine)dithiolatoplatinum(II) divergent complexes—whereby only one N atom from the “back-to-back” diimine ligand actually coordinates to a Pt(II) center in a non-bridging monodentate manner—vis-à-vis the hitherto well-studied [Pt(N^N)(S^S)] (κ2-diimine)dithiolatoplatinum(II) convergent congeners—whereby both the diimine and dithiolate coordinate as κ2-chelating bidentate. Thus, in pursuit of using luminescent building blocks to generate light-harvesting supramolecular coordination compounds, we report the synthesis, characterization, and reactivity of Pt(pyz)2(mnt), 1, in high yield (pyz = pyrazine, mnt = maleonitriledithiolate). The complex exhibits solvent-dependent exchange of the pyrazine ligands, which can be utilized in the formation of larger complexes containing platinum dithiolate moieties. As proof of concept, 1 has been converted into the more inert Pt(4,4ʹ-bpy)2(mnt), 2, and Pt(4-ap)2(mnt), 3, (4-ap = 4-aminopyridine) complexes. These complexes exhibit redox properties, are strong absorbers of ultraviolet and visible light, and exhibit bright-luminescence at 77 K. Single-crystal X-ray diffraction analysis for 1 and 3 confirms the monotopic coordination of the ligands with intramolecular Pt-S and Pt-N bond lengths being comparable to other complexes of type (κ2-diimine)(dithiolate)Pt(II), whereas significant torsion is exhibited by the two heterocyclic rings due to the lack of tethering to one another. Solvent-dependent stability is uncovered for 1 crystals, whereas the crystal structure of 3 reveals an interesting supramolecular quadrangle resulting from hydrogen bonding between the amine groups of two complexes and two interstitial water molecules. A commentary is presented to contrast the electronic structure of the diver
{"title":"Luminescent, Redox-Active Dithiolatobis(imine)platinum(II) Divergent Complexes with Exchangeable Imine Ligands: An Experimental/Computational Study Versus Their Diiminedithiolatoplatinum(II) Convergent Congeners","authors":"Jacob B. Smith, Brooke M. Otten, Paul J. Derry, C. Browning, Kurt Bodenstedt, Jessie H. Sandridge, Nisa T. Satumtira, Mina Zilaie, Jon Payne, R. Nuti, M. Omary, B. Smucker","doi":"10.1080/02603594.2019.1594205","DOIUrl":"https://doi.org/10.1080/02603594.2019.1594205","url":null,"abstract":"This article provides a third manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the journal’s identity as a niche for “critical discussion” of contemporary literature in inorganic chemistry. (For the first and second manifestations, see: (1) Otten, B. M.; Melancon, K. M.; Omary, M. A. “All that Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers: A Tribute to Al Cotton on the 10th Anniversary of His Passing,” Comments Inorg. Chem. 2018, 38, 1–35; (2) Yaseen, W. K.; Sanders, S. F.; Almotawa, R. M.; Otten, B. M.; Bhat, S.; Alamo, D. C.; Marpu, S. B.; Golden, T. D.; Omary, M. A. “Are Metal Complexes ‘Organic’, ‘Inorganic’, ‘Organometallic’, or ‘Metal-Organic’ Materials? A Case Study for the Use of Trinuclear Coinage Metal Complexes as ‘Metal-Organic Coatings’ for Corrosion Suppression on Aluminum Substrates,” Comments Inorg. Chem. 2019, 39, 1–26.) Herein, we contrast the electronic structure of two categories of Pt(II) complexes with mixed imine/thiolato ligands: a new class of [Pt(N^N)2(S^S)] bis(κ1-diimine)dithiolatoplatinum(II) divergent complexes—whereby only one N atom from the “back-to-back” diimine ligand actually coordinates to a Pt(II) center in a non-bridging monodentate manner—vis-à-vis the hitherto well-studied [Pt(N^N)(S^S)] (κ2-diimine)dithiolatoplatinum(II) convergent congeners—whereby both the diimine and dithiolate coordinate as κ2-chelating bidentate. Thus, in pursuit of using luminescent building blocks to generate light-harvesting supramolecular coordination compounds, we report the synthesis, characterization, and reactivity of Pt(pyz)2(mnt), 1, in high yield (pyz = pyrazine, mnt = maleonitriledithiolate). The complex exhibits solvent-dependent exchange of the pyrazine ligands, which can be utilized in the formation of larger complexes containing platinum dithiolate moieties. As proof of concept, 1 has been converted into the more inert Pt(4,4ʹ-bpy)2(mnt), 2, and Pt(4-ap)2(mnt), 3, (4-ap = 4-aminopyridine) complexes. These complexes exhibit redox properties, are strong absorbers of ultraviolet and visible light, and exhibit bright-luminescence at 77 K. Single-crystal X-ray diffraction analysis for 1 and 3 confirms the monotopic coordination of the ligands with intramolecular Pt-S and Pt-N bond lengths being comparable to other complexes of type (κ2-diimine)(dithiolate)Pt(II), whereas significant torsion is exhibited by the two heterocyclic rings due to the lack of tethering to one another. Solvent-dependent stability is uncovered for 1 crystals, whereas the crystal structure of 3 reveals an interesting supramolecular quadrangle resulting from hydrogen bonding between the amine groups of two complexes and two interstitial water molecules. A commentary is presented to contrast the electronic structure of the diver","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"9 1","pages":"188 - 215"},"PeriodicalIF":5.4,"publicationDate":"2019-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82714762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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