The synthesis of the first linear coordinated CuIIcomplex Cu{N(SiMe3)Dipp}2(
A Copper(II)‐Nitrite Complex Hydrogen‐Bonded to a Protonated Amine in the Second‐Coordination‐Sphere
Nitrous acid (HONO) plays pivotal roles in various metal‐free as well as metal‐mediated routes relevant to biogeochemistry, atmospheric chemistry, and mammalian physiology. While the metastable nature of HONO hinders the detailed investigations into its reactivity at a transition metal site, this report herein utilizes a heteroditopic copper(II) cryptate [
- Award ID(s):
- 1847926
- PAR ID:
- 10367578
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- European Journal of Inorganic Chemistry
- Volume:
- 2022
- Issue:
- 15
- ISSN:
- 1434-1948
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract 1 Dipp=C6H5‐2,6Pri 2) and its CuIcounterpart [Cu{N(SiMe3)Dipp}2]−(2 ) is described. The formation of1 proceeds through a dispersion force‐driven disproportionation, and is the reaction product of a CuIhalide and LiN(SiMe3)Dipp in a non‐donor solvent. The synthesis of2 is accomplished by preventing the disproportionation into1 by using the complexing agent 15‐crown‐5. EPR spectroscopy of1 provides the first detailed study of a two‐coordinate transition‐metal complex indicating strong covalency in the Cu−N bonds. -
more » « less
Abstract Low‐temperature reaction of the tris(pyrazolyl)borate copper(II) hydroxide [iPr2TpCu]2(μ‐OH)2with triphenylsilane under a dinitrogen atmosphere gives the bridging dinitrogen complex [iPr2TpCu]2(μ‐1,2‐N2) (
3 ). X‐ray crystallography reveals an only slightly activated N2ligand (N‐N: 1.111(6) Å) that bridges between two monovalentiPr2TpCu fragments. While DFT studies of mono‐ and dinuclear copper dinitrogen complexes suggest weak π‐backbonding between the d10CuIcenters and the N2ligand, they reveal a degree of cooperativity in the dinuclear Cu‐N2‐Cu interaction. Addition of MeCN, CNAr2,6‐Me, or O2to3 releases N2with formation ofiPr2TpCu(L) (L=NCMe, CNAr2,6‐Me2) or [iPr2TpCu]2(μ‐η2:η2‐O2) (1 ). Addition of triphenylsilane to [iPr2TpCu]2(μ‐OH)2in pentane allows isolation of a key intermediate [iPr2TpCu]2(μ‐H) (5 ). Although5 thermally decays under N2to give3 , it reduces unsaturated substrates, such as CO and HC≡CPh to HC(O)H and H2C=CHPh, respectively. -
null (Ed.)The crystal structures of three bridged bimetallic molecular compounds, namely, triaqua-2κ 3 O -μ-fluorido-pentafluorido-1κ 5 F -(1,10-phenanthroline-2κ 2 N , N ′)copper(II)titanium(IV) monohydrate, [Cu(TiF 6 )(phen)(H 2 O) 3 ]·H 2 O (phen is 1,10-phenanthroline, C 12 H 8 N 2 ), (I), triaqua-2κ 3 O -μ-fluorido-pentafluorido-1κ 5 F -(1,10-phenanthroline-2κ 2 N , N ′)copper(II)zirconium(IV) monohydrate, [Cu(ZrF 6 )(phen)(H 2 O) 3 ]·H 2 O, (II), and triaqua-2κ 3 O -μ-fluorido-pentafluorido-1κ 5 F -(1,10-phenanthroline-2κ 2 N , N ′)copper(II)hafnium(IV) monohydrate, [Cu(HfF 6 )(phen)(H 2 O) 3 ]·H 2 O, (III), and one molecular salt, bis[diaquafluorido(1,10-phenanthroline-κ 2 N , N ′)copper(II)] hexafluoridohafnate(IV) dihydrate, [CuF(phen)(H 2 O) 2 ] 2 [HfF 6 ]·2H 2 O, (IV), are reported. The bridged bimetallic compounds adopt Λ-shaped configurations, with the octahedrally coordinated copper(II) center linked to the fluorinated early transition metal via a fluoride linkage. The extended structures of these Λ-shaped compounds are organized through both intra- and intermolecular hydrogen bonds and intermolecular π–π stacking. The salt compound [Cu(phen)(H 2 O) 2 F] 2 [HfF 6 ]·H 2 O displays an isolated square-pyramidal Cu(phen)(H 2 O) 2 F + complex linked to other cationic complexes and isolated HfF 6 2− anions through intermolecular hydrogen-bonding interactions.more » « less
-
more » « less
A CuIIcoordination polymer,
catena -poly[[[aquacopper(II)]-bis(μ-4-aminobenzoato)-κ2N :O ;κ2O :N ] monohydrate], {[Cu(p ABA)2(H2O)]·H2O}n (p ABA =p -aminobenzoate, C7H4NO2−), was synthesized and characterized. It exhibits a one-dimensional chain structure extended into a three-dimensional supramolecular assembly through hydrogen bonds and π–π interactions. While the twinned crystal shows a metrically orthorhombic lattice and an apparent space groupPbcm , the true symmetry is monoclinic (space groupP 2/c ), with disordered Cu atoms and mixed roles of water molecules (aqua ligand/crystallization water). The luminescence spectrum of the complex shows an emission at 345 nm,cf. 349 nm forp ABAH. -
null (Ed.)We report the hydrothermal syntheses and crystal structures of aquabis(2,2′-bipyridine-κ 2 N , N ′)copper(II) hexafluoridosilicate tetrahydrate, [Cu(bpy) 2 (H 2 O)][SiF 6 ]·4H 2 O (bpy is 2,2′-bipyridine, C 10 H 8 N 2 ), (I), bis(2,2′-bipyridine-3κ 2 N , N ′)-di-μ-fluorido-1:3κ 2 F : F ;2:3κ 2 F : F -decafluorido-1κ 5 F ,2κ 5 F -ditantalum(V)copper(II), [Cu(bpy) 2 (TaF 6 ) 2 ], (II), tris(2,2′-bipyridine-κ 2 N , N ′)copper(II) bis[hexafluoridotantalate(V)], [Cu(bpy) 3 ][TaF 6 ] 2 , (III), and catena -poly[[diaqua(2,2′-bipyridine-κ 2 N , N ′)copper(II)]-μ-fluorido-tetrafluoridotin-μ-fluorido], [Cu(bpy)(H 2 O) 2 SnF 6 ] n , (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C 2 , D 2 , and D 3 symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O—H...F and O—H...O hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin.more » « less
