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1. Reductive cleavage of N , N ′-di- tert -butylcarbodiimide generates tert -butylcyanamide ligands, (Me ₃ CNCN) ⁻ , that bind potassium both end-on and side-on in the same single crystal

   https://doi.org/10.1107/S205698902000732X  

   Chung, Amanda B.; Ziller, Joseph W.; Evans, William J. (July 2020, Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   N , N ′-Di- tert -butylcarbodiimide, Me 3 CN=C=NCMe 3 , undergoes reductive cleavage in the presence of the Gd II complex, [K(18-crown-6) 2 ][Gd II (N R 2 ) 3 ] ( R = SiMe 3 ), to form a new type of ligand, the tert -butylcyanamide anion, (Me 3 CNCN) − . This new ligand can bind metals with one or two donor atoms as demonstrated by the isolation of a single crystal containing potassium salts of both end-on and side-on bound tert -butylcyanamide anions, (Me 3 CNCN) − . The crystal contains [K(18-crown-6)(H 2 O)][NCNCMe 3 - kN ], in which one ( t BuNCN) − anion is coordinated end-on to potassium ligated by 18-crown-6 and water, as well as [K(18-crown-6)][η 2 -NCNCMe 3 ], in which an 18-crown-6 potassium is coordinated side-on to the terminal N—C linkage. This single crystal also contains one equivalent of 1,3-di- tert -butyl urea, (C 9 H 20 N 2 O), which is involved in hydrogen bonding that may stabilize the whole assembly, namely, aqua( tert -butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)–( tert -butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)– N , N ′-di- tert -butylcarbodiimide (1/1/1) [K(C 5 H 9 N 2 )(C 12 H 24 O 6 )]·[K(C 5 H 9 N 2 )(C 12 H 24 O 6 )(H 2 O)]·C 9 H 20 N 2 . 

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2. Synthesis and reactivity of a nickel( ii ) thioperoxide complex: demonstration of sulfide-mediated N ₂ O reduction

   https://doi.org/10.1039/C8SC02536C  

   Hartmann, Nathaniel J.; Wu, Guang; Hayton, Trevor W. (January 2018, Chemical Science)

   The “masked” terminal nickel sulfide [K(18-crown-6)][L^tBuNi^II(S)] mediates the reduction of N₂O by CO,viathe thioperoxide complex [K(18-crown-6)][L^tBuNi^II(η²-SO)]. 

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3. The importance of the counter-cation in reductive rare-earth metal chemistry: 18-crown-6 instead of 2,2,2-cryptand allows isolation of [Y ^II (NR ₂ ) ₃ ] ¹⁻ and ynediolate and enediolate complexes from CO reactions

   https://doi.org/10.1039/C9SC05794C  

   Ryan, Austin J.; Ziller, Joseph W.; Evans, William J. (February 2020, Chemical Science)

   The use of 18-crown-6 (18-c-6) in place of 2.2.2-cryptand (crypt) in rare earth amide reduction reactions involving potassium has proven to be crucial in the synthesis of Ln( ii ) complexes and isolation of their CO reduction products. The faster speed of crystallization with 18-c-6 appears to be important. Previous studies have shown that reduction of the trivalent amide complexes Ln(NR 2 ) 3 (R = SiMe 3 ) with potassium in the presence of 2.2.2-cryptand (crypt) forms the divalent [K(crypt)][Ln II (NR 2 ) 3 ] complexes for Ln = Gd, Tb, Dy, and Tm. However, for Ho and Er, the [Ln(NR 2 ) 3 ] 1− anions were only isolable with [Rb(crypt)] 1+ counter-cations and isolation of the [Y II (NR 2 ) 3 ] 1− anion was not possible under any of these conditions. We now report that by changing the potassium chelator from crypt to 18-crown-6 (18-c-6), the [Ln(NR 2 ) 3 ] 1− anions can be isolated not only for Ln = Gd, Tb, Dy, and Tm, but also for Ho, Er, and Y. Specifically, these anions are isolated as salts of a 1 : 2 potassium : crown sandwich cation, [K(18-c-6) 2 ] 1+ , i.e. [K(18-c-6) 2 ][Ln(NR 2 ) 3 ]. The [K(18-c-6) 2 ] 1+ counter-cation was superior not only in the synthesis, but it also allowed the isolation of crystallographically-characterizable products from reactions of CO with the [Ln(NR 2 ) 3 ] 1− anions that were not obtainable from the [K(crypt)] 1+ analogs. Reaction of CO with [K(18-c-6) 2 ][Ln(NR 2 ) 3 ], generated in situ , yielded crystals of the ynediolate products, {[(R 2 N) 3 Ln] 2 (μ-OCCO)} 2− , which crystallized with counter-cations possessing 2 : 3 potassium : crown ratios, i.e. {[K 2 (18-c-6) 3 ]} 2+ , for Gd, Dy, Ho. In contrast, reaction of CO with a solution of isolated [K(18-c-6) 2 ][Gd(NR 2 ) 3 ], produced crystals of an enediolate complex isolated with a counter-cation with a 2 : 2 potassium : crown ratio namely [K(18-c-6)] 2 2+ in the complex [K(18-c-6)] 2 {[(R 2 N) 2 Gd 2 (μ-OCHCHO) 2 ]}. 

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4. Site‐Specific Reduction‐Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb ⁺ Complexation

   https://doi.org/10.1002/anie.202115747  

   Zhou, Zheng; Fernández‐García, Jesús M.; Zhu, Yikun; Evans, Paul J.; Rodríguez, Rafael; Crassous, Jeanne; Wei, Zheng; Fernández, Israel; Petrukhina, Marina A.; Martín, Nazario (December 2021, Angewandte Chemie International Edition)

   Abstract The chemical reduction of π‐conjugated bilayer nanographene1(C₁₃₈H₁₂₀) with K and Rb in the presence of 18‐crown‐6 affords [K⁺(18‐crown‐6)(THF)₂][{K⁺(18‐crown‐6)}₂(THF)_0.5][C₁₃₈H₁₂₂³⁻] (2) and [Rb⁺(18‐crown‐6)₂][{Rb⁺(18‐crown‐6)}₂(C₁₃₈H₁₂₂³⁻)] (3). Whereas K⁺cations are fully solvent‐separated from the trianionic core thus affording a “naked”1^.3−anion, Rb⁺cations are coordinated to the negatively charged layers of1^.3−. According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site‐specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction‐induced site‐specific hydrogenation provokes dramatic changes in the (electronic) structure of1as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers. 

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5. Synthesis of Crystallographically Characterizable Bis(cyclopentadienyl) Sc(II) Complexes: (C ₅ H ₂ ^t Bu ₃ ) ₂ Sc and {[C ₅ H ₃ (SiMe ₃ ) ₂ ] ₂ ScI} ^1–

   https://doi.org/10.1021/jacs.3c11922  

   Queen, Joshua D.; Anderson-Sanchez, Lauren M.; Stennett, Cary R.; Rajabi, Ahmadreza; Ziller, Joseph W.; Furche, Filipp; Evans, William J. (February 2024, Journal of the American Chemical Society)

   The synthesis of previously unknown bis(cyclopentadienyl) complexes of the first transition metal, i.e., Sc(II) scandocene complexes, has been investigated using C5H2(tBu)3 (Cpttt), C5Me5 (Cp*), and C5H3(SiMe3)2 (Cp″) ligands. Cpttt 2ScI, 1, formed from ScI3 and KCpttt, can be reduced with potassium graphite (KC8) in hexanes to generate dark-red crystals of the first crystallographically characterizable bis(cyclopentadienyl) scandium(II) complex, Cpttt 2Sc, 2. Complex 2 has a 170.6° (ring centroid)-Sc-(ring centroid) angle and exhibits an eight-line EPR spectrum characteristic of Sc(II) with Aiso = 82.6 MHz (29.6 G). It sublimes at 200 °C at 10−4 Torr and has a melting point of 268−271 °C. Reductions of Cp*2ScI and Cp″2ScI under analogous conditions in hexanes did not provide new Sc(II) complexes, and reduction of Cp*2ScI in benzene formed the Sc(III) phenyl complex, Cp*2Sc(C6H5), 3, by C−H bond activation. However, in Et2O and toluene, reduction of Cp*2ScI at −78 °C gives a dark-red solution, 4, which displays an eight-line EPR pattern like that of 1, but it did not provide thermally stable crystals. Reduction of Cp″2ScI, in THF or Et2O at −35 °C in the presence of 2.2.2-cryptand, yields the green Sc(II) metallocene iodide complex, [K(crypt)][Cp″2ScI], 5, which was identified by X-ray crystallography and EPR spectroscopy and is thermally unstable. The analogous reaction of Cp*2ScI with KC8 and 18-crown-6 in Et2O gave the ligand redistribution product, [Cp*2Sc(18- crown-6-κ2O,O′)][Cp*2ScI2], 6, as the only crystalline product. Density functional theory 

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