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1. Site-selective halogenation of mixed-valent vanadium oxide clusters

   https://doi.org/10.1039/D0DT01077D  

   Maiola, Michela L.; Petel, Brittney E.; Brennessel, William W.; Matson, Ellen M. (January 2020, Dalton Transactions)

   Here, we expand on the synthesis and characterization of chloride-functionalized polyoxovanadate-alkoxide (POV-alkoxide) clusters, to include the halogenation of mixed-valent vanadium oxide assemblies. These findings build on our previously disclosed results describing the preparation of a mono-anionic chloride-functionalized cluster, [V 6 O 6 Cl(OC 2 H 5 ) 12 ] 1− , by chlorination of [V 6 O 7 (OC 2 H 5 ) 12 ] 2− with AlCl 3 , aimed at understanding the electronic consequences of the introduction of halide-defects in bulk metal oxides ( e.g. VO 2 ). While chlorination of the mixed-valent POV-ethoxide clusters was not possible using AlCl 3 , we have found that the chloride-substituted oxidized derivatives of the Lindqvist vanadium-oxide clusters can be formed using TiCl 3 (thf) 3 with [V 6 O 7 (OC 2 H 5 ) 12 ] n ( n = 1−, 0) or WCl 6 with [V 6 O 7 (OC 2 H 5 ) 12 ] 0 . Characterization of the chloride-containing products, [V 6 O 6 Cl(OC 2 H 5 ) 12 ] n ( n = 0, 1+), was accomplished via 1 H NMR spectroscopy, X-ray crystallography, and elemental analysis. Electronic analysis of the redox series of Cl-doped POV-alkoxide clusters via infrared and electronic absorption spectroscopies revealed all redox events are localized to the vanadyl portion of the cluster, with the site differentiated V III –Cl moiety retaining its reduced oxidation state across a 1.9 V window. These results present new synthetic routes for accessing chloride-doped POV-alkoxide clusters from mixed-valent vanadium oxide precursors. 

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2. Wire like diplatinum, triplatinum, and tetraplatinum complexes featuring X[PtCCCCCCCC] _m PtX segments; iterative syntheses and functionalization for measurements of single molecule properties

   https://doi.org/10.1039/C9DT00870E  

   Zheng, Qinglin; Schneider, Jakob F.; Amini, Hashem; Hampel, Frank; Gladysz, John A. (April 2019, Dalton Transactions)

   Reaction of ( p -tol 3 P) 2 PtCl 2 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/THF/reflux) gives monosubstituted trans -Cl( p -tol 3 P) 2 Pt(CC) 2 SiMe 3 (63%), which with wet n -Bu 4 N + F − yields trans -Cl( p -tol 3 P) 2 Pt(CC) 2 H ( 2 , 96%). Hay oxidative homocoupling (O 2 /CuCl/TMEDA) gives all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 Cl ( 3 , 68%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 1/rt) affords monosubstituted all- trans -Cl( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (46%), which is converted by a similar desilylation/homocoupling sequence to all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 3 Pt(P p -tol 3 ) 2 Cl ( 7 ; 79%). Reaction of ( p -tol 3 P) 2 PtCl 2 and excess H(CC) 2 SiMe 3 (HNEt 2 /cat. CuI) gives trans -Me 3 Si(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 (78%), which with wet n -Bu 4 N + F − affords trans -H(CC) 2 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Hay oxidative cross coupling with 2 (1 : 4) gives all- trans -Cl[( p -tol 3 P) 2 Pt(CC) 4 ] 2 Pt(P p -tol 3 ) 2 Cl ( 10 , 36%) along with homocoupling product 3 (33%). Reaction of 3 and Me 3 Sn(CC) 2 SiMe 3 (1 : 2/rt) yields all- trans -Me 3 Si(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 SiMe 3 ( 17 , 77%), which with wet n -Bu 4 N + F − gives all- trans -H(CC) 2 ( p -tol 3 P) 2 Pt(CC) 4 Pt(P p -tol 3 ) 2 (CC) 2 H (96%). Reaction of 3 and excess Me 3 P gives all- trans -Cl(Me 3 P) 2 Pt(CC) 4 Pt(PMe 3 ) 2 Cl ( 4 , 86%). A model reaction of trans -( p -tol)( p -tol 3 P) 2 PtCl and KSAc yields trans -( p -tol)( p -tol 3 P) 2 PtSAc ( 12 , 75%). Similar reactions of 3 , 7 , 10 , and 4 give all- trans -AcS[(R 3 P) 2 Pt(CC) 4 ] n Pt(PR 3 ) 2 SAc (76–91%). The crystal structures of 3 , 17 , and 12 are determined. The first exhibits a chlorine–chlorine distance of 17.42 Å; those in 10 and 7 are estimated as 30.3 Å and 43.1 Å. 

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3. 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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4. 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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5. The reaction of thiourea and 1,3-dimethylthiourea towards organoiodines: oxidative bond formation and halogen bonding

   https://doi.org/10.1107/S205322962100869X  

   Peloquin, Andrew J.; Ragusa, Arianna C.; McMillen, Colin D.; Pennington, William T. (October 2021, Acta Crystallographica Section C Structural Chemistry)

   By varying the halogen-bond-donor molecule, 11 new halogen-bonding cocrystals involving thiourea or 1,3-dimethylthiourea were obtained, namely, 1,3-dimethylthiourea–1,2-diiodo-3,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 1 , thiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·CH 4 N 2 S, 2 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 3 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–methanol (1/1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S·CH 4 O, 4 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–ethanol (1/1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S·C 2 H 6 O, 5 , 1,3-dimethylthiourea–1,4-diiodo-2,3,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 6 , 1,3-dimethylthiourea–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 3 H 8 N 2 S, 7 , 1,3-dimethylthiourea–1,1,2,2-tetraiodoethene (1/1), C 6 H 16 N 4 S 2 ·C 2 I 4 , 8 , [(dimethylamino)methylidene](1,2,2-triiodoethenyl)sulfonium iodide–1,1,2,2-tetraiodoethene–acetone (1/1/1), C 5 H 8 I 3 N 2 S + ·I − ·C 3 H 6 O·C 2 I 4 , 9 , 2-amino-4-methyl-1,3-thiazol-3-ium iodide–1,1,2,2-tetraiodoethene (2/3), 2C 4 H 7 N 2 S + ·2I − ·3C 2 I 4 , 10 , and 4,4-dimethyl-4 H -1,3,5-thiadiazine-3,5-diium diiodide–1,1,2,2-tetraiodoethene (2/3), 2C 5 H 12 N 4 S 2+ ·4I − ·3C 2 I 4 , 11 . When utilizing the common halogen-bond-donor molecules 1,2-, 1,3-, and 1,4-diiodotetrafluorobenzene, as well as 1,3,5-trifluoro-2,4,6-triiodobenzene, bifurcated I...S...I interactions were observed, resulting in the formation of isolated rings, chains, and sheets. Tetraiodoethylene (TIE) provided I...S...I cocrystals as well, but further yielded a sulfonium-containing product through the reaction of the S atom with TIE. This particular sulfonium motif is the first of its kind to be structurally characterized, and is stabilized in the solid state through a three-dimensional I...I halogen-bonding network. Thiourea reacted with acetone in the presence of TIE to provide two novel heterocyclic products, again stabilized in the solid state through I...I halogen bonding. 

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