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1. Structural diversity in copper(I) iodide complexes with 6-thioxopiperidin-2-one, piperidine-2,6-dithione and isoindoline-1,3-dithione ligands

   https://doi.org/10.1107/S2056989020009676  

   Wheaton, Amelia M. ; Guzei, Ilia A. ; Berry, John F. ( August 2020 , Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   Copper(I) iodide complexes are well known for displaying a diverse array of structural features even when only small changes in ligand design are made. This structural diversity is well displayed by five copper(I) iodide compounds reported here with closely related piperidine-2,6-dithione (SNS), isoindoline-1,3-dithione (SNS6), and 6-thioxopiperidin-2-one (SNO) ligands: di-μ-iodido-bis[(acetonitrile-κ N )(6-sulfanylidenepiperidin-2-one-κ S )copper(I)], [Cu 2 I 2 (CH 3 CN) 2 (C 5 H 7 NOS) 2 ] ( I ), bis(acetonitrile-κ N )tetra-μ 3 -iodido-bis(6-sulfanylidenepiperidin-2-one-κ S )- tetrahedro -tetracopper(I), [Cu 4 I 4 (CH 3 CN) 4 (C 5 H 7 NOS) 4 ] ( II ), catena -poly[[(μ-6-sulfanylidenepiperidin-2-one-κ 2 O : S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NOS)] n ( III ), poly[[(piperidine-2,6-dithione-κ S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NS 2 )] n ( IV ), and poly[[(μ-isoindoline-1,3-dithione-κ 2 S : S )copper(I)]-μ 3 -iodido], [CuI(C 8 H 5 NS 2 )] n ( V ). Compounds I and II crystallize as discrete dimeric and tetrameric complexes, whereas III , IV , and V crystallize as polymeric two-dimensional sheets. To the best of our knowledge, compound III is the first instance of an extended hexagonal [Cu 3 I 3 ] structure that is not supported by bridging ligands. Structures I , II , and IV display weak to moderately strong Cu...Cu cuprophilic interactions [Cu...Cu internuclear distances range between 2.5803 (10) and 2.8485 (14) Å]. All structures except III display weak hydrogen-bonding interactions between the N—H of the ligand and the μ 2 and μ 3 -I − atoms. Structure III contains classical N–H...O interactions between the SNO ligands that connect the molecules in a three-dimensional framework. Complex V features π–π stacking interactions between the aryl rings of the SNS6 ligands within the same polymeric sheet. In structure IV , there were three partially occupied solvent molecules of dichloromethane and one partially occupied molecule of acetonitrile present in the asymmetric unit. The SQUEEZE routine [Spek (2015). Acta Cryst . C 71 , 9–18] was used to correct the diffraction data for diffuse scattering effects and to identify the solvent molecules. The given chemical formula and other crystal data do not take into account the solvent molecules. 

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2. Crystallographic characterization of rare-earth cyanotriphenylborate complexes and the cyanoborates [NCBPh 3 ] 1− , [NCBPh 2 Me] 1− , and [NCBPh 2 (μ-O)BPh 2 ] 1−

   https://doi.org/10.1107/S2056989021006861  

   Dumas, Megan T. ; White, Jessica R. ; Ziller, Joseph W. ; Evans, William J. ( August 2021 , Acta Crystallographica Section E Crystallographic Communications)

   The investigation of the coordination chemistry of rare-earth metal complexes with cyanide ligands led to the isolation and crystallographic characterization of the Ln III cyanotriphenylborate complexes dichlorido(cyanotriphenylborato-κ N )tetrakis(tetrahydrofuran-κ O )lanthanide(III), [ Ln Cl 2 (C 19 H 15 BN)(C 4 H 8 O) 4 ] [lanthanide ( Ln ) = dysprosium (Dy) and yttrium Y)] from reactions of LnCl 3 , KCN, and NaBPh 4 . Attempts to independently synthesize the tetraethylammonium salt of (NCBPh 3 ) − from BPh 3 and [NEt 4 ][CN] in THF yielded crystals of the phenyl-substituted cyclic borate, tetraethylazanium 2,2,4,6-tetraphenyl-1,3,5,2λ 4 ,4,6-trioxatriborinan-2-ide, C 8 H 20 N + ·C 24 H 20 B 3 O 3 − or [NEt 4 ][B 3 (μ-O) 3 (C 6 H 5 ) 4 ]. The mechanochemical reaction of BPh 3 and [NEt 4 ][CN] without solvent produced crystals of tetraethylazanium cyanodiphenyl-λ 4 -boranyl diphenylborinate, C 8 H 20 N + ·C 25 H 20 B 2 NO − or [NEt 4 ][NCBPh 2 (μ-O)BPh 2 ]. Reaction of BPh 3 and KCN in THF in the presence of 2.2.2-cryptand (crypt) led to a crystal of bis[(2.2.2-cryptand)potassium] 2,2,4,6-tetraphenyl-1,3,5,2λ 4 ,4,6-trioxatriborinan-2-ide cyanomethyldiphenylborate tetrahydrofuran disolvate, 2C 18 H 36 KN 2 O 6 + ·C 24 H 20 B 3 O 3 − ·C 14 H 13 BN − ·2C 4 H 8 O or [K(crypt)] 2 [B 3 (μ-O) 3 (C 6 H 5 ) 4 ][NCBPh 2 Me]·2THF. The [NCBPh 2 (μ-O)BPh 2 ] 1− and (NCBPh 2 Me) 1− anions have not been structurally characterized previously. The structure of 1-Y was refined as a two-component twin with occupancy factors 0.513 (1) and 0.487 (1). In 4 , one solvent molecule was disordered and included using multiple components with partial site-occupancy factors. 

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3. Synthesis and crystallographic characterization of diphenylamide rare-earth metal complexes Ln (NPh 2 ) 3 (THF) 2 and [(Ph 2 N) 2 Ln (μ-NPh 2 )] 2

   https://doi.org/10.1107/S2056989020009998  

   Palumbo, Chad T. ; Kotyk, Christopher M. ; Ziller, Joseph W. ; Evans, William J. ( September 2020 , Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   Studies of the coordination chemistry between the diphenylamide ligand, NPh 2 , and the smaller rare-earth Ln III ions, Ln = Y, Dy, and Er, led to the structural characterization by single-crystal X-ray diffraction crystallography of both solvated and unsolvated complexes, namely, tris(diphenylamido-κ N )bis(tetrahydrofuran-κ O )yttrium(III), Y(NPh 2 ) 3 (THF) 2 or [Y(C 12 H 10 N) 3 (C 4 H 8 O) 2 ], 1-Y , and the erbium(III) (Er), 1-Er , analogue, and bis[μ-1κ N :2(η 6 )-diphenylamido]bis[bis(diphenylamido-κ N )yttrium(III)], [(Ph 2 N) 2 Y(μ-NPh 2 )] 2 or [Y 2 (C 12 H 10 N) 6 ], 2-Y , and the dysprosium(III) (Dy), 2-Dy , analogue. The THF ligands of 1-Er are modeled with disorder across two positions with occupancies of 0.627 (12):0.323 (12) and 0.633 (7):0.367 (7). Also structurally characterized was the tetrametallic Er III bridging oxide hydrolysis product, bis(μ-diphenylamido-κ 2 N : N )bis[μ-1κ N :2(η 6 )-diphenylamido]tetrakis(diphenylamido-κ N )di-μ 3 -oxido-tetraerbium(III) benzene disolvate, {[(Ph 2 N)Er(μ-NPh 2 )] 4 (μ-O) 2 }·(C 6 H 6 ) 2 or [Er 4 (C 12 H 10 N) 8 O 2 ]·2C 6 H 6 , 3-Er . The 3-Er structure was refined as a three-component twin with occupancies 0.7375:0.2010:0.0615. 

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4. Phosphorus-based ligand effects on the structure and radical scavenging ability of molecular nanoparticles of CeO 2

   https://doi.org/10.1039/d1dt02667d  

   Russell-Webster, Bradley ; Lopez-Nieto, Javi ; Abboud, Khalil A. ; Christou, George ( November 2021 , Dalton Transactions)

   Two new Ce IV /O 2− clusters, (pyH) 8 [Ce 10 O 4 (OH) 4 (O 3 PPh) 12 (NO 3 ) 12 ] (1) and [Ce 6 O 4 (OH) 4 (O 2 PPh 2 ) 4 (O 2 C t Bu) 8 ] (2), have been prepared that contain P-based ligands for the first time. They were obtained from the reaction of (NH 4 ) 2 [Ce(NO 3 ) 6 ], PhPO 3 H 2 or Ph 2 PO 2 H, and t BuCO 2 H in a 2 : 1 : 2 molar ratio in pyridine/MeOH (10 : 1 mL). Both compounds contain a {Ce 6 O 4 (OH) 4 } face-capped octahedral core, with 1 containing an additional four Ce IV on the outside to give a supertetrahedral Ce 10 topology; the {Ce 6 O 8 } unit is the smallest recognizable fragment of the fluorite structure of CeO 2 . The HO˙ radical scavenging activities of 1 and 2 were measured by UV/vis spectral monitoring of methylene blue oxidation by HO˙ radicals in the presence and absence of the Ce/O clusters, and the results compared with those for larger Ce 24 and Ce 38 molecular nanoparticles of CeO 2 prepared in previous work. 1 and 2 are both very poor HO˙ radical scavengers compared with Ce 24 and Ce 38 , a result that is consistent with reports in the literature that PO 4 3− ions inhibit the radical scavenging ability of traditional CeO 2 nanoparticles and putatively assigned to PO 4 3− binding to the surface. 

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5. Reactivity of Ce( iv ) imido compounds with heteroallenes

   https://doi.org/10.1039/C9CC10052K  

   Lapsheva, Ekaterina N. ; Cheisson, Thibault ; Álvarez Lamsfus, Carlos ; Carroll, Patrick J. ; Gau, Michael R. ; Maron, Laurent ; Schelter, Eric J. ( April 2020 , Chemical Communications)

   null (Ed.)

   The reactivity of alkali metal capped Ce( iv ) imido compounds [M(DME) 2 ][CeNAr F (TriNOx)] ( 1-M with M = K, Rb, Cs and Ar F = 3,5-bis(trifluoromethyl)phenyl) with CO 2 and organic isocyanates has been evaluated. 1-Cs reacted with CO 2 to yield an organocarbamate complex. Reaction of 1-K and 1-Rb with organic isocyanates yielded organoureate Ce( iv ) complexes. 

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