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1. In crystallo homolytic cleavage of a terminal lanthanum( iii )–methyl bond by Cu Kα X-radiation forms a La( ii ) complex

   https://doi.org/10.1039/D5CC04945H  

   Stennett, Cary R; Luevano, Makayla R; Ziller, Joseph W; Evans, William J (January 2026, Chemical Communications)

   A new La(ii) synthesis involves SCXRD experiments on the La(iii) methyl complex La(SAr^iPr6)₂CH₃, Ar^iPr6= C₆H₃-2,6-(C₆H₂-2,4,6-ⁱPr₃)₂, with Cu Kα X-rays that results in homolytic La-CH₃cleavage and formation of the La(ii) complex La(SAr^iPr6)₂. 

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2. Exploring sulfur donor atom coordination chemistry with La( ii ), Nd( ii ), and Tm( ii ) using a terphenylthiolate ligand

   https://doi.org/10.1039/d4cc01037j  

   Gilbert-Bass, Kito; Stennett, Cary R.; Grotjahn, Robin; Ziller, Joseph W.; Furche, Filipp; Evans, William J. (April 2024, Chemical Communications)

   To expand the range of donor atoms known to stabilize 4fⁿ5d¹Ln(ii) ions beyond C, N, and O first row main group donor atoms, the Ln(iii) terphenylthiolate iodides, Ln^III(SAr^iPr6)₂I (Ar^iPr6= C₆H₃-2,6-(C₆H₂-2,4,6-ⁱPr₃)₂, Ln = La, Nd) were reduced to Ln^II(SAr^iPr6)₂complexes. 

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3. Ynamide and Azaalleneyl. Acid‐Base Promoted Chelotropic and Spin‐State Rearrangements in a Versatile Heterocumulene [(Ad)NCC( ^t Bu)] ⁻

   https://doi.org/10.1002/anie.202401433  

   Russell, John B; Jafari, Mehrafshan G; Kim, Jun‐Hyeong; Pudasaini, Bimal; Ozarowski, Andrew; Telser, Joshua; Baik, Mu‐Hyun; Mindiola, Daniel J (May 2024, Angewandte Chemie International Edition)

   Abstract We introduce the heterocumulene ligand [(Ad)NCC(^tBu)]⁻(Ad=1‐adamantyl (C₁₀H₁₅),^tBu=tert‐butyl, (C₄H₉)), which can adopt two forms, the azaalleneyl and ynamide. This ligand platform can undergo a reversible chelotropic shift using Brønsted acid‐base chemistry, which promotes an unprecedented spin‐state change of the [V^III] ion. These unique scaffolds are prepared via addition of 1‐adamantyl isonitrile (C≡NAd) across the alkylidyne in complexes [(BDI)V≡C^tBu(OTf)] (A) (BDI⁻=ArNC(CH₃)CHC(CH₃)NAr), Ar=2,6‐ⁱPr₂C₆H₃) and [(dBDI)V≡C^tBu(OEt₂)] (B) (dBDI²⁻=ArNC(CH₃)CHC(CH₂)NAr). ComplexAreacts with C≡NAd, to generate the high‐spin [V^III] complex with a κ¹‐N‐ynamide ligand, [(BDI)V{κ¹‐N‐(Ad)NCC(^tBu)}(OTf)] (1). Conversely,Breacts with C≡NAd to generate a low‐spin [V^III] diamagnetic complex having a chelated κ²‐C,N‐azaalleneyl ligand, [(dBDI)V{κ²‐N,C‐(Ad)NCC(^tBu)}] (2). Theoretical studies have been applied to better understand the mechanism of formation of2and the electronic reconfiguration upon structural rearrangement by the alteration of ligand denticity between1and2. 

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4. A closed-shell monomeric rhenium(1−) anion provided by m -terphenyl isocyanide ligation

   https://doi.org/10.1039/d0cc03043k  

   Salsi, Federico; Neville, Michael; Drance, Myles; Hagenbach, Adelheid; Chan, Chinglin; Figueroa, Joshua S.; Abram, Ulrich (January 2020, Chemical Communications)

   The mixed isocyanide/carbonyl complexes cis - and trans -[Re(CO) 3 Br(CNAr Dipp2 ) 2 ] (Ar Dipp2 = 2,6-(2,6-(i-Pr) 2 C 6 H 3 ) 2 C 6 H 3 ) can be synthesized from reactions of [Re(CO) 5 Br] and CNAr Dipp2 depending on the conditions applied. Reduction of the neutral Re( i ) species gives the monoanionic complex [Re(CO) 3 (CNAr Dipp2 ) 2 ] − or the neutral [Re(CO) 3 (CNAr Dipp2 ) 2 ], which contain rhenium in the formal oxidation states “−1” and “0”, respectively. 

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5. Metallacyclobuta‐(2,3)‐diene: A Bidentate Ligand for Stream‐line Synthesis of First Row Transition Metal Catalysts for Cyclic Polymerization of Phenylacetylene

   https://doi.org/10.1002/anie.202318956  

   Russell, John B; Konar, Debabrata; Keller, Taylor M; Gau, Michael R; Carroll, Patrick J; Telser, Joshua; Lester, Daniel W; Veige, Adam S; Sumerlin, Brent S; Mindiola, Daniel J (February 2024, Angewandte Chemie International Edition)

   Not, available (Ed.)

   Abstract Described here is a direct entry to two examples of 3d transition metal catalysts that are active for the cyclic polymerization of phenylacetylene, namely, [(BDI)M{κ²‐C,C‐(Me₃SiC₃SiMe₃)}] (2‐M) (BDI=[ArNC(CH₃)]₂CH⁻, Ar=2,6‐ⁱPr₂C₆H₃;M=Ti, V). Catalysts are prepared in one step by the treatment of [(BDI)MCl₂] (1‐M,M=Ti,V) with 1,3‐dilithioallene [Li₂(Me₃SiC₃SiMe₃)]. Complexes2‐Mhave been spectroscopically and structurally characterized and the polymers that are catalytically formed from phenylacetylene were verified to have a cyclic topology based on a combination of size‐exclusion chromatography (SEC) and intrinsic viscosity studies. Two‐electron oxidation of2‐Vwith nitrous oxide (N₂O) cleanly yields a [V^V] alkylidene‐alkynyl oxo complex [(BDI)V(=O){κ¹‐C‐(=C(SiMe₃)CC(SiMe₃))}] (3), which lends support for how this scaffold in2‐Mmight be operating in the polymerization of the terminal alkyne. This work demonstrates how alkylidynes can be circumvented using 1,3‐dianionic allene as a segue into M−C multiple bonds. 

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