The crystal structure of the title compound, hexaaquanickel(II) dichloride–1,4,7,10,13,16-hexaoxacyclooctadecane–water (1/2/2), [Ni(H2O)6]Cl2·2C12H24O6·2H2O, is reported. The asymmetric unit contains half of the Ni(OH2)6moiety with a formula of C12H32ClNi0.50O10at 105 K and triclinic (P1) symmetry. The [Ni(OH2)6]2+cation has close to ideal octahedral geometry with O—Ni—O bond angles that are within 3° of idealized values. The supramolecular structure includes hydrogen bonding between the water ligands, 18-crown-6 molecules, Cl−anions, and co-crystallized water solvent. Two crown ether molecules flank the [Ni(OH2)6]2+molecule at the axial positions in a sandwich-like structure. The relatively symmetric hydrogen-bonding network is enabled by small Cl−counter-ions and likely influences the more idealized octahedral geometry of [Ni(OH2)6]2+.
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H 2 evolution from H 2 O via O–H oxidative addition across a 9,10-diboraanthracene
The water reactivity of the boroauride complex ([Au(B 2 P 2 )][K(18-c-6)]; (B 2 P 2 , 9,10-bis(2-(diisopropylphosphino)-phenyl)-9,10-dihydroboranthrene) and its corresponding two-electron oxidized complex, Au(B 2 P 2 )Cl, are presented. Au(B 2 P 2 )Cl is tolerant to H 2 O and forms the hydroxide complex Au(B 2 P 2 )OH in the presence of H 2 O and triethylamine. [Au(B 2 P 2 )]Cl and [Au(B 2 P 2 )]OH are poor Lewis acids as judged by the Gutmann–Becket method, with [Au(B 2 P 2 )]OH displaying facile hydroxide exchange between B atoms of the DBA ring as evidenced by variable temperature NMR spectroscopy. The reduced boroauride complex [Au(B 2 P 2 )] − reacts with 1 equivalent of H 2 O to produce a hydride/hydroxide product, [Au(B 2 P 2 )(H)(OH)] − , that rapidly evolves H 2 upon further H 2 O reaction to yield the dihydroxide compound, [Au(B 2 P 2 )(OH) 2 ] − . [Au(B 2 P 2 )]Cl can be regenerated from [Au(B 2 P 2 )(OH) 2 ] − via HCl·Et 2 O, providing a synthetic cycle for H 2 evolution from H 2 O enabled by O–H oxidative addition at a diboraanthracene unit.
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- Award ID(s):
- 1752876
- PAR ID:
- 10214775
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 56
- Issue:
- 89
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 13804 to 13807
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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