Review
Chemistry, Inorganic & Nuclear
Alec Bigness, Shivaiah Vaddypally, Michael J. Zdilla, Jose L. Mendoza-Cortes
Summary: Heterocubane is a molecular species with a cube-shaped core found in nature, playing a crucial role in important biological reactions. Limited reviews have focused on the significance of the cluster outside of biology, or on the impact of the global coordination environment on reactivity and electronic structure. Understanding the synthetic chemistry of heterocubanes in the context of coordination environment and geometry offers insights into their connection to natural systems.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Organic
Caroline R. Pharr, Brian J. Esselman, Robert J. McMahon
Summary: This study experimentally verified the specific chemical reaction process of 1-(3-thienyl)diazoethane through photolysis, exploring its relationship with hydrogen migration and quantum mechanical tunneling effects.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jiping Hao, Akihide Nishiyama, Shigeki Mori, Ko Furukawa, Soji Shimizu
Summary: The oxidation of tetra-beta-arylated 5,15-dioxaporphyrin was studied, and stepwise oxidation from the 20π-electron neutral state to the 19π-electron radical cation and 18π-electron dication was achieved. Further oxidation of the 18π-aromatic dication resulted in the formation of a ring-opened dipyrrindione product. The results demonstrate the ring-opening reactivity of oxaporphyrinium cation species, similar to heme degradation in nature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Electrochemistry
Edgar A. Reyes Cruz, Daiki Nishiori, Brian L. Wadsworth, Diana Khusnutdinova, Timothy Karcher, Gautier Landrot, Benedikt Lassalle-Kaiser, Gary F. Moore
Summary: A novel binuclear Fe(III) fused porphyrin was synthesized and characterized in this study, with ultraviolet-visible spectroscopy confirming its extended electronic structure. Fourier transform infrared spectroscopy indicated the iron centers in this fused porphyrin experience a relatively rigid ligand environment compared to a structurally related mononuclear complex. Electrochemical measurements showed a doubling of the number of redox events associated with the fused, binuclear complex compared to the mononuclear porphyrin.
Review
Chemistry, Organic
Virginie Carreras, Nour Tanbouza, Thierry Ollevier
Summary: The use of iron catalysis in reactions involving diazo compounds has become increasingly popular, offering a valuable alternative to toxic and expensive metal catalysts. Iron-mediated reactions have shown great potential in forging carbon-carbon or carbon-heteroatom bonds through insertion reactions, ylide formation, and other methods.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Yoshihiro Ishimaru, Fumiya Takahashi, Samu Mochizuki, Natsuki Hosoda, Takashi Fujihara
Summary: In this study, two isomeric bis(dicarbonylrhodium(I)) complexes, one with a syn configuration and the other with an anti configuration, were successfully isolated and characterized. The analysis revealed significant differences in their structures and properties.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jonathan Trouve, Paolo Zardi, Shaymaa Al-Shehimy, Thierry Roisnel, Rafael Gramage-Doria
Summary: Utilizing secondary interactions between substrates and catalysts is a promising approach to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are often discovered through trial-and-error screening, as small stereo-electronic modifications within the substrate and catalyst can lead to vastly different reactivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, Sophie Maguire, Claire Donohoe, John E. O'Brien, Brendan Twamley, Ligia C. Gomes-da-Silva, Mathias O. Senge
Summary: Inspired by 'picket-fence' systems, this study utilized strain to introduce intramolecular tension, leading to selective compound atropisomer conversion and the formation of distinctive supramolecular nanostructures.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Inorganic & Nuclear
Donghyun Jeong, Joan Selverstone Valentine, Jaeheung Cho
Summary: Metalloenzymes use transition metal ions as co-factors to bind with dioxygen, allowing it to be used in various biological processes. Metal-peroxo species have been proposed as key intermediates, and synthetic model chemistry has helped understand their mechanisms. This review focuses on nonheme first-row transition metal peroxo complexes with their physicochemical characterization, structural information, and chemical reactivities relevant to biological systems.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, John E. O'Brien, Daire J. Gibbons, Mathias O. Senge
Summary: This study sheds light on the fundamental issue of atropisomerism in porphyrins, using benzenesulfonic acid for host-guest interactions and NMR spectroscopy to characterize all four rotamers. The research suggests that charge-assisted complexation is key to unraveling the atropisomeric enigma in porphyrinoids. Additionally, X-ray structural analysis was used to investigate weak host-guest interactions in nonplanar porphyrins.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Hai-Xu Wang, Liangliang Wu, Bin Zheng, Lili Du, Wai-Pong To, Cheng-Hoi Ko, David Lee Phillips, Chi-Ming Che
Summary: In this study, the hydrogen atom transfer reactivity of an Fe porphyrin nitrido species towards C-H substrates was investigated using nanosecond laser flash photolysis. It was found that C-H bonds with bond dissociation enthalpies of up to approximately 84 kcal mol(-1) could be activated, with second-order rate constants on the order of 10(2)-10(4) s(-1) m(-1). The Fe-amido product formed after hydrogen atom transfer could further release ammonia upon protonation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jireh Joy D. Sacramento, Therese Albert, Maxime Siegler, Pierre Moenne-Loccoz, David P. Goldberg
Summary: A new ferrous corrole complex [Fe-II(ttppc)](-) has been shown to bind dioxygen to form Fe-O-2, exhibiting an O-16/18(2)-isotope sensitive n(O-O) stretch at 1128 cm(-1) and a single n(Fe-O-2) at 555 cm(-1). This complex can mediate the dioxygenation of an indole derivative and extract hydrogen atoms from activated O-H bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Environmental Sciences
Yong Liu, Jie Ma, Jiaoli Gao, Xingyi Chen, Xiaoxue Ouyang, Liping Weng, Haiming Li, Yali Chen, Yongtao Li
Summary: This study investigates the interaction and heteroaggregation of biochar nanoparticles (BCNPs) and iron mineral nanoparticles (IMNPs) in soil remediation. The results demonstrate that pH, humic acid (HA), and ionic strength (IS) play significant roles in the settling and stability of nanoparticles.
Article
Chemistry, Multidisciplinary
Maksym Matviyishyn, Agata Bialonska, Bartosz Szyszko
Summary: Crownphyrins are a class of hybrid macrocycles combining structural features of porphyrin and crown ethers. They possess the ability to bind neutral and ionic guests. The presence of dynamic covalent imine linkages connecting the dipyrrin segment with the ether chain enables unusual coordination behavior of crownphyrins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Sara Gutierrez, Maria Tomas-Gamasa, Jose L. Mascarenas
Summary: Implementing catalytic organometallic transformations in living settings can provide unprecedented opportunities in chemical biology and medicine. This study demonstrated the feasibility of metal carbene transfer reactions in live mammalian cells, highlighting the potential for expanding the repertoire of life-compatible abiotic reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Joseph J. Gair, Yehao Qiu, Rahul L. Khade, Natalie H. Chan, Alexander S. Filatov, Yong Zhang, Jared C. Lewis
Article
Chemistry, Multidisciplinary
David A. Vargas, Rahul L. Khade, Yong Zhang, Rudi Fasan
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Physical
Rahul L. Khade, Ajay L. Chandgude, Rudi Fasan, Yong Zhang
Article
Chemistry, Multidisciplinary
Erwin G. Abucayon, Rahul L. Khade, Douglas R. Powell, Yong Zhang, George B. Richter-Addo
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Multidisciplinary
Yelu Shi, Matthew A. Michael, Yong Zhang
Summary: This work elucidates the basic mechanism of the nonheme enzyme-mediated conversion of HNO to NO, resolving longstanding debates on reversibility and uncovering the reasons for the irreversible nature of this conversion. The study also identifies the first thermodynamically favorable and kinetically feasible mechanism for the experimental reverse reaction, providing insights that will aid in further related studies and the development of HNO probes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Rahul L. Khade, Erwin G. Abucayon, Douglas R. Powell, George B. Richter-Addo, Yong Zhang
Summary: NO binding to ferrous and ferric hemes results in different effects on the axial trans Fe-L bond length, with a shortening observed in ferric hemes. This difference is attributed to the absence of a strong sigma antibonding interaction in Fe(III) systems. Additionally, the spin state of the systems is lowered upon NO binding, providing a rationale for the observed bond shortening in Fe(III) but not Fe(II) derivatives.
Article
Chemistry, Multidisciplinary
Yang Wei, Melissa Conklin, Yong Zhang
Summary: Engineered heme protein biocatalysts provide an efficient and sustainable approach for the synthesis of amine-containing compounds through C-H amination. A quantum chemical study reveals that nitrene formation is the rate-determining step in the overall reaction, and the catalyst with a serine ligand exhibits the highest reactivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yelu Shi, Gianna Stella, Jia-Min Chu, Yong Zhang
Summary: This study reveals the importance of HNO binding and a proton-coupled electron transfer mechanism for HNO reaction through quantum chemical research on Cu cyclams. The results indicate that steric effect is the primary factor, and electronic factor is the secondary factor, but the combined effects can lead to unexpected reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Biochemistry & Molecular Biology
Yong Zhang, Jia-Min Chu
Summary: Engineered heme proteins have been developed for efficient biocatalytic nitrenoid C-H functionalizations. Computational methods such as DFT, QM/MM, and MD calculations have been used to understand the mechanistic aspects of these reactions. This review summarizes the recent advances in computational reaction pathway studies, focusing on the reactivity, regioselectivity, enantioselectivity, diastereoselectivity, and the effects of substrate, ligand, metal center, and protein environment. The common and distinctive mechanistic features of these reactions are also discussed, along with future perspectives.
Article
Chemistry, Multidisciplinary
Shiliang Tian, Ruixi Fan, Therese Albert, Rahul L. Khade, Huiguang Dai, Kevin A. Harnden, Parisa Hosseinzadeh, Jing Liu, Mark J. Nilges, Yong Zhang, Pierre Moenne-Loccoz, Yisong Guo, Yi Lu
Summary: This study successfully achieved stepwise nitrosylation of a mononuclear nonheme iron site in an engineered azurin under physiological conditions, controlled formation of {FeNO}(7) and {Fe(NO)(2)}(9) species by tuning the nitric oxide equivalents and reaction time. The potential formation of the elusive {FeNO}(8) species was inferred by EPR spectroscopy, while the conversion of {FeNO}(7) to {Fe(NO)(2)}(9) species was supported by various spectroscopic techniques.
Article
Chemistry, Inorganic & Nuclear
Erwin G. Abucayon, Jia-Min Chu, Megan Ayala, Rahul L. Khade, Yong Zhang, George B. Richter-Addo
Summary: The study investigated the binding preference of nitrosoarenes to heme proteins through X-ray crystallography and density functional theory analysis, revealing a preference for N-binding to ferrous heme centers and O-binding to ferric hemes. Results were rationalized based on energy levels of spin-states, with dp-pp* and ds-pp* identified as the dominant stabilization forces for the observed N-coordination and O-coordination, respectively. This study provides a first-time explanation for why oxidation of ferrous-ArNO compound to its ferric state leads to subsequent ligand dissociation.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Dhanashree Selvan, Yelu Shi, Pallavi Prasad, Skyler Crane, Yong Zhang, Saumen Chakraborty
DALTON TRANSACTIONS
(2020)