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1. A cationic gold-fluorenyl complex with a dative Au → C + bond: synthesis, structure, and carbophilic reactivity

   https://doi.org/10.1039/D2CC05436A  

   Litle, Elishua D. ; Gabbaï, François P. ( January 2023 , Chemical Communications)

   Aiming to study the interaction of gold with the highly Lewis acidic fluorenyl cation, we synthesised ( o -[Ph 2 P(C 6 H 4 )Flu)AuCl(tht)][BF 4 ] ([2][BF 4 ]) and ( o -Ph 2 P(C 6 H 4 )Flu)AuCl 2 (3) (Flu = 9-fluorenyl) and found that the latter could be converted into [( o -Ph 2 P(C 6 H 4 )Flu)AuCl] + ([4] + ) upon treatment with NaBArF 24 (BArF 24 = B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ). [4] + , which has been isolated as a chloride-bridged dimer, readily catalyses the cycloisomerisation of 2-allyl-2-(2-propynyl)malonate. Computational results show that [4] + possesses a strong Au → C + bond and readily activates enynes. 

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2. 5-([( Z )-Methoxyimino]{2-[(2-methylphenoxy)methyl]phenyl}methyl)-1,3,4-oxadiazole-2(3 H )-thione dimethyl sulfoxide monosolvate

   https://doi.org/10.1107/S2414314623002377  

   Shripanavar, Chetan Shrimandhar ; Balerao, Rishik ; Butcher, Ray J. ( March 2023 , IUCrData)

   The title compound, C 18 H 17 N 3 O 3 S·C 2 H 6 OS, crystallizes in the monoclinic space group P 2 1 /c . In the crystal, C 1 1 (9) chains of C—H...O interactions are formed, propogating in the c -axis direction. The N—H hydrogen atom forms a strong hydrogen bond with the oxygen atom of a DMSO solvate molecule. 

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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. O -Benzoyl side-chain conformations in 2,3,4,6-tetra- O -benzoyl-β- D -galactopyranosyl-(1→4)-1,2,6-tri- O -benzoyl-β- D -glucopyranose (ethyl acetate solvate) and 1,2,4,6-tetra- O -benzoyl-β- D -glucopyranose (acetone solvate)

   https://doi.org/10.1107/S2053229619000822  

   Turney, Toby ; Pan, Qingfeng ; Zhang, Wenhui ; Oliver, Allen G. ; Serianni, Anthony S. ( February 2019 , Acta Crystallographica Section C Structural Chemistry)

   The crystal structures of 2,3,4,6-tetra- O -benzoyl-β-D-galactopyranosyl-(1→4)-1,2,6-tri- O -benzoyl-β-D-glucopyranose ethyl acetate hemisolvate, C 61 H 50 O 18 ·0.5C 4 H 8 O 2 , and 1,2,4,6-tetra- O -benzoyl-β-D-glucopyranose acetone monosolvate, C 34 H 28 O 10 ·C 3 H 6 O, were determined and compared to those of methyl β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside (methyl β-lactoside) and methyl β-D-glucopyranoside hemihydrate, C 7 H 14 O 6 ·0.5H 2 O, to evaluate the effects of O -benzoylation on bond lengths, bond angles and torsion angles. In general, O -benzoylation exerts little effect on exo- and endocyclic C—C and endocyclic C—O bond lengths, but exocyclic C—O bonds involved in O -benzoylation are lengthened by 0.02–0.04 Å depending on the site of substitution. The conformation of the O -benzoyl side-chains is highly conserved, with the carbonyl O atom either eclipsing the H atom attached to a 2°-alcoholic C atom or bisecting the H—C—H bond angle of an 1°-alcoholic C atom. Of the three bonds that determine the side-chain geometry, the C—O bond involving the alcoholic C atom exhibits greater rotational variability than the remaining C—O and C—C bonds involving the carbonyl C atom. These findings are in good agreement with recent solution NMR studies of the O -acetyl side-chain conformation in saccharides. 

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5. Bis(catecholato-κ 2 O , O ′)bis(dimethyl sulfoxide-κ O )titanium(IV)

   https://doi.org/10.1107/S2056989022002638  

   Hewage, Nisansala ; Mastriano, Carolyn ; Brückner, Christian ; Zeller, Matthias ( April 2022 , Acta Crystallographica Section E Crystallographic Communications)

   Bis(benzene-1,2-diolato-κ 2 O , O ′)bis(dimethyl sulfoxide-κ O )titanium(IV), [Ti(C 6 H 4 O 2 ) 2 (C 2 H 6 OS) 2 ], crystallizes with two crystallographically independent molecules in the space group P 2 1 / c emulating orthorhombic Pbca symmetry (β = 90.0445 (9)°]. The two molecules are related by pseudo-glide symmetry, broken by modulation of each one catecholate and dimethyl sulfoxide (DMSO) ligand. Twinning by pseudomerohedry was observed [twin ratio 0.5499 (7):0.4401 (7)]. Complex 3 was obtained by heating of diprotonated titanium tris-catecholate precursor 2 H in DMSO, by formal displacement of a catechol molecule by two DMSO molecules. Complex 3 is just the second heteroleptic, mono-nuclear, neutral bis-catecholate complex with TiO 6 metal coordination, the only other one being its bis-DMF analogue 6 . The two molecules of 3 exhibit a distorted octahedral geometry. The geometry and distortions from ideal symmetry of 3 are discussed and compared to 6 and to cationic tris-catecholate titanium complexes. 

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