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1. 2.2.2-Cryptand complexes of neptunium( iii ) and plutonium( iii )

   https://doi.org/10.1039/D1CC05904A  

   Goodwin, Conrad A.; Ciccone, Sierra R.; Bekoe, Samuel; Majumdar, Sourav; Scott, Brian L.; Ziller, Joseph W.; Gaunt, Andrew J.; Furche, Filipp; Evans, William J. (January 2022, Chemical Communications)

   New coordination environments are reported for Np( iii ) and Pu( iii ) based on pilot studies of U( iii ) in 2.2.2-cryptand (crypt). The U( iii )-in-crypt complex, [U(crypt)I 2 ][I], obtained from the reaction between UI 3 and crypt, is treated with Me 3 SiOTf (OTf = O 3 SCF 3 ) in benzene to form the [U(crypt)(OTf) 2 ][OTf] complex. Similarly, the isomorphous Np( iii ) and Pu( iii ) complexes were obtained similarly starting from [AnI 3 (THF) 4 ]. All three complexes (1-An; An = U, Np, Pu) contain an encapsulated actinide in a THF-soluble complex. Absorption spectroscopy and DFT calculations are consistent with 5f 3 U( iii ), 5f 4 Np( iii ), and 5f 5 Pu( iii ) electron configurations. 

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2. Unusually short Au( iii )⋯Au( iii ) aurophilic contacts between anions. Necessity of counterions

   https://doi.org/10.1039/D5DT00879D  

   Scheiner, Steve; Michalczyk, Mariusz; Zierkiewicz, Wiktor (June 2025, Dalton Transactions)

   The occurrence of these anion⋯anion dimers in the crystal structure are dependent on the presence of counterions as the attraction between two Au(iii) centers is insufficient to override the coulombic repulsion. 

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3. Synthesis and characterization of thermoplastic poly(piperazine succinate) metallopolymers coordinated to ruthenium( III ) or iron( III )

   https://doi.org/10.1002/pol.20220583  

   Schneider, Jessica K.; Ove, Clarissa A.; Pirlo, Russell K.; Biffinger, Justin C. (November 2022, Journal of Polymer Science)

   Abstract Metal‐containing polymers represent an ever‐expanding frontier of material science. Of the numerous biocompatible ligands used to create a metallopolymer, piperazine‐containing polymers are still in their early development, even though piperazine is a common functional group in drug design and bioengineering scaffolding elements. We report the first synthesis and characterization (with NMR, IR, GPC, UV–vis spectroscopy, and thermal analysis) of two thermoplastic poly(alkyl piperazine succinate) diols with either propyl or hexyl alkane chains bridging the piperazines. These polyester diols were then chain extended with hexamethylene diisocyanate to create highly amorphous polyester urethane thermoplastic polymers. Ru(III) or Fe(III) was then successfully coordinated with these polymers, with approximately 30% of the bulk metallopolymer product becoming 250x the molecular weight of the non‐metal containing polymers. However, coordination of Fe(III), and to a lesser extent Ru(III), to these polypiperazines accelerated the hydrolysis of the polyester linkage in water over 15 days. Thus, these novel polymers are highly biodegradable with Fe(III) metallopolymers hydrolyzing faster than Ru(III) metallopolymers and poly(propyl piperazine succinate) polymers hydrolyzing faster than poly(hexyl piperazine succinate) polymers. 

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4. A mononuclear, terminal titanium( iii ) imido

   https://doi.org/10.1039/d3cc01758c  

   Mohar, Jacob S; Reinholdt, Anders; Keller, Taylor M; Carroll, Patrick J; Telser, Joshua; Mindiola, Daniel J (August 2023, Chemical Communications)

   We report the first mononuclear Ti^IIIcomplex possessing a terminal imido ligand. 

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5. Solution and solid-state characterization of rare silyluranium( iii ) complexes

   https://doi.org/10.1039/d4cc00655k  

   Lin, Nathan J.; Zeller, Matthias; Bart, Suzanne C. (April 2024, Chemical Communications)

   A uranium(iii) silylate complex [K(DME)₄]-[UI₂{(Si(SiMe₃)₂SiMe₂)₂O}] (1) was stabilized by the addition of 18-crown-6 to form [K(18-crown-6)][UI₂{(Si(SiMe₃)₂SiMe₂)₂O}]. This species was fully characterized using multinuclear NMR spectroscopy, electronic absorption spectroscopy and X-ray crystallography. 

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