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1. Synthesis of Cationic Molybdenum Imido 2-Adamantylidene Complexes from Bispyrrolides via Cationic Pyrrolenine Complexes

   https://doi.org/10.1021/acs.organomet.1c00415  

   Paul, Bhaskar; Schrock, Richard R.; Tsay, Charlene (September 2021, Organometallics)
2. Mechanochemistry of Cationic Cobaltocenium Mechanophore

   https://doi.org/10.1021/jacs.1c05233  

   Cha, Yujin; Zhu, Tianyu; Sha, Ye; Lin, Huina; Hwang, JiHyeon; Seraydarian, Matthew; Craig, Stephen L.; Tang, Chuanbing (August 2021, Journal of the American Chemical Society)
3. Cationic Bis(Gold) Indenyl Complexes

   https://doi.org/10.1002/cplu.202300691  

   Slinger, Brady_L; Zhu, Jiaqi; Widenhoefer, Ross_A (February 2024, ChemPlusChem)

   Abstract Reaction of (P)AuOTf [P=P(t‐Bu)₂o‐biphenyl] with indenyl‐ or 3‐methylindenyl lithium led to isolation of gold η¹‐indenyl complexes (P)Au(η¹‐inden‐1‐yl) (1 a) and (P)Au(η¹‐3‐methylinden‐1‐yl) (1 b), respectively, in >65 % yield. Whereas complex1 bis static, complex1 aundergoes facile, degenerate 1,3‐migration of gold about the indenyl ligand (ΔG^≠_153K=9.1±1.1 kcal/mol). Treatment of complexes1 aand1 bwith (P)AuNTf₂led to formation of the corresponding cationic bis(gold) indenyl complexestrans‐[(P)Au]₂(η¹,η¹‐inden‐1,3‐yl) (2 a) andtrans‐[(P)Au]₂(η¹,η²‐3‐methylinden‐1‐yl) (2 b), respectively, which were characterized spectroscopically and modeled computationally. Despite the absence of aurophilic stabilization in complexes2 aand2 b, the binding affinity of mono(gold) complex1 atoward exogenous (P)Au⁺exceed that of free indene by ~350‐fold and similarly the binding affinity of1 btoward exogenous (P)Au⁺exceed that of 3‐methylindene by ~50‐fold. The energy barrier for protodeauration of bis(gold) indenyl complex2 awith HOAc was ≥8 kcal/mol higher than for protodeauration of mono(gold) complex1 a. 

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4. A Cationic Magnesium-Based Dithiolene Radical

   https://doi.org/10.1021/acs.organomet.1c00607  

   Wang, Yuzhong; Tran, Phuong M.; Dzikovski, Boris; Xie, Yaoming; Wei, Pingrong; Rains, April A.; Asadi, Hamid; Ramasamy, Ramaraja P.; Schaefer, Henry F.; Robinson, Gregory H. (March 2022, Organometallics)
5. Catalytic asymmetric cationic shifts of aliphatic hydrocarbons

   https://doi.org/10.1038/s41586-023-06826-7  

   Wakchaure, Vijay N.; DeSnoo, William; Laconsay, Croix J.; Leutzsch, Markus; Tsuji, Nobuya; Tantillo, Dean J.; List, Benjamin (January 2024, Nature)

   Abstract Asymmetric catalysis is an advanced area of chemical synthesis, but the handling of abundantly available, purely aliphatic hydrocarbons has proven to be challenging. Typically, heteroatoms or aromatic substructures are required in the substrates and reagents to facilitate an efficient interaction with the chiral catalyst. Confined acids have recently been introduced as tools for homogenous asymmetric catalysis, specifically to enable the processing of small unbiased substrates¹. However, asymmetric reactions in which both substrate and product are purely aliphatic hydrocarbons have not previously been catalysed by such super strong and confined acids. We describe here an imidodiphosphorimidate-catalysed asymmetric Wagner–Meerwein shift of aliphatic alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity. Despite their long history and high relevance for chemical synthesis and biosynthesis, Wagner–Meerwein reactions utilizing purely aliphatic hydrocarbons, such as those originally reported by Wagner and Meerwein, had previously eluded asymmetric catalysis. 

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