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1. 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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2. A Complete Triad of Zero‐Valent 17‐Electron Monoradicals of Group 7 Elements Stabilized by m ‐Terphenyl Isocyanides

   https://doi.org/10.1002/anie.202300254  

   Salsi, Federico; Wang, Shuai; Teutloff, Christian; Busse, Marvin; Neville, Michael L.; Hagenbach, Adelheid; Bittl, Robert; Figueroa, Joshua S.; Abram, Ulrich (April 2023, Angewandte Chemie International Edition)

   Abstract The first consistent series of mononuclear 17‐electron complexes of three Group 7 elements has been isolated in crystalline form and studied by X‐ray diffraction and spectroscopic methods. The paramagnetic compounds have a composition of [M⁰(CO)(CNp‐F‐Ar^DArF2)₄] (M=Mn, Tc, Re; Ar^DArF2=2,6‐(3,5‐(CF₃)₂C₆H₃)₂C₆H₂F) and are stabilized by four sterically encumbering isocyanides, which prevent the metalloradicals from dimerization. They have a square pyramidal structure with the carbonyl ligands as apexes. The frozen‐solution EPR spectra of the rhenium and technetium compounds are clearly anisotropic with large⁹⁹Tc and^185,187Re hyperfine interactions for one component. High‐field EPR (Q band and W band) has been applied for the elucidation of the EPR parameters of the manganese(0) complex. 

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3. 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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4. 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 (April 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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5. A Triply Negatively Charged Nanographene Bilayer with Spin Frustration

   https://doi.org/10.1002/anie.202217788  

   Wang, Wenqing; Ma, Xiao‐Hui; Liu, Min; Tang, Shuxuan; Ding, Xuguang; Zhao, Yue; Tan, Yuan‐Zhi; Kertesz, Miklos; Wang, Xinping (January 2023, Angewandte Chemie International Edition)

   Abstract We report on the largest open‐shell graphenic bilayer and also the first example of triply negatively charged radical π‐dimer. Upon three‐electron reduction, bilayer nanographene fragment molecule (C₉₆H₂₄Ar₆)₂(Ar=2,6‐dimethylphenyl) (1₂) was transformed to a triply negatively charged species1₂^3.−, which has been characterized by single‐crystal X‐ray diffraction, electron paramagnetic resonance (EPR) spectroscopy and magnetic properties on a superconducting quantum interference device (SQUID).1₂^3.−features a 96‐center‐3‐electron (96c/3e) pancake bond with a doublet ground state, which can be thermally excited to a quartet state. It consists of 34 π‐fused rings with 96 conjugatedsp²carbon atoms. Spin frustration is observed with the frustration parameterf>31.8 at low temperatures in1₂^3.−, which indicates graphene upon reduction doping may behave as a quantum spin liquid. 

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