Article
Chemistry, Multidisciplinary
Malte Fischer, Matthew M. D. Roy, Lewis L. Wales, Mathias A. Ellwanger, Caitilin McManus, Aisling F. Roper, Andreas Heilmann, Simon Aldridge
Summary: A systematic study on stable stannaimines was conducted by combining different heteroleptic stannylenes with organic azides. The reactions yielded new stannaimines with varied reactivity profiles, including activation of substrates under ambient conditions and rare examples of main group multiple bond metathesis reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Inorganic & Nuclear
Roman Jambor, Miroslav Novak
Summary: Low-valent N-coordinated cations and dications of heavier group 14 elements exhibit ambiphilic character, acting as ligands in transition metal chemistry and replacing catalysts based on transition metal complexes in chemical transformations.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Kritika Gour, Milan Kumar Bisai, Sakya S. Sen
Summary: Recent studies have utilized the sterically demanding hypersilyl group to stabilize unusual compounds with group 14 elements. These compounds are significant in terms of their structure and reactivity, and show potential for small molecule activation under ambient conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Masahito Murai, Mako Ito, Satoshi Takahashi, Shigehiro Yamaguchi
Summary: Diazulenylmethyl cations bridged with a germanium and tin moiety were synthesized, and the properties of these cations were affected by the nature of these elements. Aggregated cations exhibit absorption bands in the near-infrared region, which are slightly blue-shifted compared to silicon-bridged congeners.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Debotra Sarkar, Sayan Dutta, Catherine Weetman, Emeric Schubert, Debasis Koley, Shigeyoshi Inoue
Summary: This study presents the unique electronic properties of bis-NHC stabilized germyliumylidenes and their applications in various chemical reactions, showing both Lewis basic and Lewis acid nature.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Javier A. Cabeza, Pablo Garcia-Alvarez
Summary: Two synthetic approaches have been utilized to synthesize transition metal complexes with tridentate PEP tetryl ligands. One approach involves the oxidative addition of an E-X bond (X=H, C or halogen) to a low-valent transition metal complex using tetrelanes as the metal-free precursor, while the other approach involves the insertion of an E atom into an M-X bond (X=Cl) of the metal precursor or derivatization of the E atom after coordination to the metal using tetrylenes. This review discusses the different types of PEP tetryl ligand frameworks found in transition metal complexes for each synthetic approach.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xiongfei Zheng, Agamemnon E. Crumpton, Andrey V. Protchenko, Mathias A. Ellwanger, Andreas Heilmann, Simon Aldridge
Summary: The reduction of boryl-substituted Sn-II bromide with potassium graphite leads to the generation of a cyclic tetratin tetraboryl system, which is a non-aromatic homo-metallic analogue of cyclobutadiene dianion. Abstraction of the cations or oxidation results in contraction or cleavage of the Sn-4 unit, while protonation generates a heavier homologue of cyclobutene. This study provides insights into the charge distribution and reactivity of the [Sn-4{B(NDippCH)(2)}(4)](2-) dianion.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Mujahuddin M. Siddiqui, Samir Kumar Sarkar, Mohd Nazish, Massimiliano Morganti, Christian Kohler, Jiali Cai, Lili Zhao, Regine Herbst-Irmer, Dietmar Stalke, Gernot Frenking, Herbert W. Roesky
Summary: The paper presents the first examples of donor-stabilized two-coordinate Sb(I) and Bi(I) ions, which belong to a new class of acyclic cations of Group 15. These compounds were successfully synthesized and characterized through various analytical techniques, demonstrating their potential as heavier valence isoelectronic analogues of carbones.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Tianyi Sun, Jiazhong Li, Hao Wang
Summary: This review summarizes recent achievements in the chemistry of heavier analogues of carbonyls, including synthetic approaches, structural parameters and reactivity. Heavier analogues, which are unstable, have shown potential in synthetic chemistry and have been the focus of much progress in recent years.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Shenglai Yao, Arseni Kostenko, Yun Xiong, Christian Lorent, Ales Ruzicka, Matthias Driess
Summary: Using a chelating C,C'-bis(silylenyl)-ortho-dicarborane ligand, a monoatomic zero-valent Ge complex was synthesized, showing different reactivities towards reductants and oxidants due to the redox non-innocent nature of the carborane scaffold. The reduction and oxidation of the Ge complex resulted in the formation of dianionic or dicationic bis(silylene)-supported Ge complexes with distinct properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Jonas Strecker, Bastian Pfeuffer, Alexander Hinz
Summary: Stepwise metalation and metathesis reactions were conducted to prepare derivatives of tetravalent group 14 elements. These compounds were considered as potential precursors for the formation of doubly bonded group 14/group 15 molecules. The obtained compounds were characterized by multinuclear NMR spectroscopy and SCXRD studies.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Swastik Biswas, Niranjan Patel, Rahul Deb, Moumita Majumdar
Summary: The ambiphilic Ge(II) and Sn(II) cationic species have been successfully stabilized using structurally non-rigid bis(imine) based tetradentate supporting ligands. The inherent flexibility of the ligand backbone allows for geometric rearrangements to enhance reactivity, and the bifunctionality of the ligand enables the formation of Ge(II) bis-monocations. The redox-active nature of the ligand promotes participation in chemical transformations.
Review
Chemistry, Inorganic & Nuclear
Thomas Delouche, Muriel Hissler, Pierre-Antoine Bouit
Summary: Polycyclic aromatic hydrocarbons (PAHs) are important organic building blocks for optoelectronic applications. This review focuses on the insertion of heavy group 14 elements (Si, Ge, and Sn) into the polyaromatic backbone, discussing synthetic approaches, optical and redox properties, and highlighting their insertion into optoelectronic devices.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Shailja Jain, David Danovich, Slavko Radenkovic, Sason Shaik
Summary: This study presents a valence bond analysis of Ge-3(NH)(3) and explores the entire E-3(NH)(3) series (E=C, Si, Ge, Sn, Pb). The E-3(NH)(3) rings exhibit a nonbonded structure with localized pi-lone pairs on the N atoms, unlike the aromatic carbon rings with pi-delocalization. However, these molecules have significant covalent-ionic resonance energies, indicating the presence of stabilized pi-systems through charge-shift bonding. This analysis provides insights into the structure and pi-delocalization in germanazene and its substituted derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Benjamin S. Mitchell, Werner Kaminsky, Alexandra Velian
Summary: A new strategy was reported to tailor the electronic properties of a superatomic metal chalcogenide cluster by redox matching the core with surface tin(IV) sites. Two ternary clusters were synthesized using salt metathesis, showing new electronic states attributed to the reduction of a surface tin site. X-ray diffraction analysis revealed no Sn···Se coordination in the solid state.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Mrittika Roy, Jeffrey H. Walton, James C. Fettinger, Alan L. Balch
Summary: This study reports a method for the direct synthesis of diamine radical cations in crystalline form through the oxidation of triphenylamine. The results demonstrate that two different products can be obtained depending on the oxidizing agent used.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Anna Lo, David A. Gutierrez, Garrett Toth-Williams, James C. Fettinger, Jared T. Shaw
Summary: Lewis acid mediated allylations of beta-alkoxy N-tosyl imines using allyltrimethylsilane led to the formation of anti-selective 3-alkoxy homoallylic N-tosyl amines. Two methods of Cu(OTf)(2)-mediated allylations were reported, showing that diastereoselectivity can be achieved through the 1,3 acyclic stereocontrol of beta-chiral aldimines. The observed selectivity trends and computational evidence suggest that selectivity arises through the formation of a six-membered ring chelate.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
David A. Gutierrez, James Fettinger, K. N. Houk, Kaori Ando, Jared T. Shaw
Summary: This study describes the Lewis-acid-promoted addition of prochiral E- and Z-allyl nucleophiles to chiral alpha-alkoxy N-tosyl imines with stereochemical control, resulting in the synthesis of two isomers of clausenamide.
Article
Chemistry, Physical
Ashlee K. Hauble, Caitlin M. Crawford, Jesse M. Adamczyk, Maxwell Wood, James C. Fettinger, Eric S. Toberer, Susan M. Kauzlarich
Summary: Layered Zintl phases with A2MPn2 stoichiometry are potential thermoelectric materials with complex chemistry. This study focuses on Yb2-xEuxCdSb2 solid solution and investigates the impact of defects on thermal and electronic properties. The research reveals that tuning the defect structure can significantly improve the thermoelectric performance.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Organic
Benjamin D. Bergstrom, Garrett Toth-Williams, Anna Lo, Jeffrey W. Toman, James. C. Fettinger, Jared T. Shaw
Summary: Polysubstituted allenes are valuable synthetic intermediates that offer structural complexity, modularity, and chirality for further transformations. In this study, a novel method for synthesizing tetrasubstituted allenes with geminal acyl/alkoxy substitution is reported. These unique push-pull allenes demonstrate bench-stability and interesting reactivity in various applications.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Lilia M. Baldauf, James C. Fettinger, Marilyn M. Olmstead, Kamran B. Ghiassi, Alan L. Balch
Summary: Two new cocrystals, named 1 and 2, were discovered with a clamshell arrangement of two porphyrins surrounding a central C70 molecule. Cocrystal 1 has a unique double-clamshell arrangement, while cocrystal 2 has a simple clamshell arrangement.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Rongqing Shang, Allan He, Elizabeth L. Kunz Wille, Na Hyun Jo, James C. Fettinger, Paul C. Canfield, Susan M. Kauzlarich
Summary: The solid solutions of Yb14ZnSb11 with different RE3+ elements were prepared to investigate the intermediate valency of Yb in Yb14ZnSb11. The substitution of Yb with RE3+ elements can impact the valency of Yb ions. Large crystals were grown using Sn-flux, the structure and magnetic susceptibility were studied. The results showed that all compounds crystallize in the Ca14AlSb11 structure type and the RE3+ ions exhibit a size-dependent preference for substitution at the Yb site.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Qihao Zhu, James C. Fettinger, Petra Vasko, Philip P. Power
Summary: A series of tin hydride transition metal complexes were obtained and their structures and reactivity were characterized and studied computationally.
Article
Chemistry, Inorganic & Nuclear
Connor P. McLoughlin, James C. Fettinger, Philip P. Power
Summary: Six new transition-metal aryloxides were synthesized and characterized to compare the steric and dispersive characteristics of their substituents. The results show that the -C6H2-2,4,6-Cy-3 substituent has higher dispersive energy donor properties and influences the thermal stability. Complexes 1 and 2 exhibit high thermal stability and short-contact H···H interactions, while complexes 5 and 6 have a lower association number due to the lower dispersion energy donor properties of the -OC6H3-2,6-Pr-i (2) ligand.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Alice C. Phung, James C. Fettinger, Philip P. Power
Summary: A series of ferriostannylenes with different iron and/or tin substituents were synthesized and their structures and spectroscopic properties were investigated. The results showed that the substituents have significant effects on the structure and properties of the compounds.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Leo W. T. Parsons, James C. C. Fettinger, Louise A. A. Berben
Summary: This study explores N-alkylation and N-metallation of pyridine to understand how metal-ligand complexes can mimic NAD(+) redox chemistry. The syntheses of substituted dipyrazolylpyridine (pz(2)P) compounds (pz(2)P)Me+ (1(+)) and (pz(2)P)GaCl2+ (2(+)) are reported and compared with previous transition element pz(2)P complexes. Cyclic voltammetry measurements show that cationic 1(+) and 2(+) exhibit irreversible reduction events at an anodic potential of SIM;900 mV, unlike the neutral pz(2)P complexes of divalent metals.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Mingchun Gao, Jose M. Ruiz, Emily Jimenez, Anna Lo, Croix J. Laconsay, James C. Fettinger, Dean J. Tantillo, Jared T. Shaw
Summary: Substrates designed for 1,4-C-H insertion to produce benzocyclobutenes underwent a unique elimination reaction, resulting in the formation of ortho-quinone dimethide (o-QDM) intermediates that further participated in Diels-Alder or hetero-Diels-Alder cycloadditions. The analogous benzylic acetals or ethers, on the other hand, bypassed the C-H insertion pathway and, after hydride transfer, underwent a de-aromatizing elimination reaction to form o-QDM at ambient temperature. The resulting dienes exhibited high diastereo- and regio-selectivity when involved in various cycloaddition reactions. This method represents a rare example of catalytic o-QDM generation without the involvement of a benzocyclobutene, and it offers a mild and ambient temperature approach to access these valuable intermediates. DFT calculations provided support for the proposed mechanism. Furthermore, this methodology was successfully applied to the synthesis of (+/-)-isolariciresinol with an overall yield of 41%.
Article
Chemistry, Multidisciplinary
Wenxing Zou, Kristian L. Mears, James C. Fettinger, Philip P. Power
Summary: Thermal Sn-C cleavage in diarylstannylene Sn(Ar-iPr4)(2) was used to generate radicals for alkyne arylstannylation. The reaction produced aryl vinyl stannylene complexes with different substituents and a known distannene.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Benjamin D. Bergstrom, Garrett Toth-Williams, Anna Lo, Jeffrey W. Toman, James. C. Fettinger, Jared T. Shaw
Summary: Polysubstituted allenes are important synthetic intermediates that offer structural complexity, modularity, and axial chirality in further transformations. We report the synthesis of tetrasubstituted allenes featuring a novel geminal acyl/alkoxy substitution, which exhibit both stability and interesting reactivity in several applications.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kristian L. Mears, Michelle A. Kutzleb, Cary R. Stennett, James C. Fettinger, Derrick C. Kaseman, Ping Yu, Petra Vasko, Philip P. Power
Summary: The fragmentation reactions of complex [B(beta-pinane)(3)] and its analogues were studied. It was found that the stereochemistry of the terpene greatly affects the London dispersion interactions.
CHEMICAL COMMUNICATIONS
(2022)