More Like this

1. Nickel-mediated N–N bond formation and N ₂ O liberation via nitrogen oxyanion reduction

   https://doi.org/10.1039/D1SC02846D  

   Beagan, Daniel M.; Cabelof, Alyssa C.; Pink, Maren; Carta, Veronica; Gao, Xinfeng; Caulton, Kenneth G. (August 2021, Chemical Science)

   The syntheses of (DIM)Ni(NO 3 ) 2 and (DIM)Ni(NO 2 ) 2 , where DIM is a 1,4-diazadiene bidentate donor, are reported to enable testing of bis boryl reduced N-heterocycles for their ability to carry out stepwise deoxygenation of coordinated nitrate and nitrite, forming O(Bpin) 2 . Single deoxygenation of (DIM)Ni(NO 2 ) 2 yields the tetrahedral complex (DIM)Ni(NO)(ONO), with a linear nitrosyl and κ 1 -ONO. Further deoxygenation of (DIM)Ni(NO)(ONO) results in the formation of dimeric [(DIM)Ni(NO)] 2 , where the dimer is linked through a Ni–Ni bond. The lost reduced nitrogen byproduct is shown to be N 2 O, indicating N–N bond formation in the course of the reaction. Isotopic labelling studies establish that the N–N bond of N 2 O is formed in a bimetallic Ni 2 intermediate and that the two nitrogen atoms of (DIM)Ni(NO)(ONO) become symmetry equivalent prior to N–N bond formation. The [(DIM)Ni(NO)] 2 dimer is susceptible to oxidation by AgX (X = NO 3 − , NO 2 − , and OTf − ) as well as nitric oxide, the latter of which undergoes nitric oxide disproportionation to yield N 2 O and (DIM)Ni(NO)(ONO). We show that the first step in the deoxygenation of (DIM)Ni(NO)(ONO) to liberate N 2 O is outer sphere electron transfer, providing insight into the organic reductants employed for deoxygenation. Lastly, we show that at elevated temperatures, deoxygenation is accompanied by loss of DIM to form either pyrazine or bipyridine bridged polymers, with retention of a BpinO − bridging ligand. 

   more » « less
2. Structure and magnetic characterization of some bicompartmental [N ₆ O ₂ ] divalent metal( ii ) complexes using bis(phenolato) ligands bearing two pendant bis(pyridyl) amine arms

   https://doi.org/10.1039/d3nj02380j  

   Mautner, Franz A.; Fischer, Roland C.; Torvisco, Ana; Nakashima, Kai; Handa, Makoto; Mikuriya, Masahiro; Salem, Nahed M.; Overby, Gabriel J.; Maier, Madison R.; Louka, Febee R.; et al (August 2023, New Journal of Chemistry)

   Reactions of the bicompartmental bis(phenolato) compound 6,6′-methylenebis(2-((bis(pyridin-2-ylmethyl)amino)methyl)-4-chlorophenol)hemihydrate (H 2 L ½H 2 O) with 3d metal( ii ) ions afforded novel fully structurally characterized bridged acetato dinuclear complexes [Mn 2 (HL)(μ 1,2 -OAc) 2 ]PF 6 (1) [Zn 2 (HL)(μ 1,2 -OAc)(H 2 O) 0.75 (MeOH) 0.25 ](PF 6 ) 2 ·0.45(H 2 O) (5) and [Cd 2 (HL)(μ 1,1,2 -OAc)(OAc)(H 2 O)]PF 6 ·H 2 O (6) as well as the polymeric bridged-azido tetranuclear catena -[Cu 4 (HL) 2 (μ 1,1 -N 3 ) 2 (μ 1,3 -N 3 ) 2 ](NO 3 ) 2 ·5H 2 O (4). The complex [Cu 4 (HL) 2 (ClO 4 ) 3 (H 2 O) 5 ](ClO 4 ) 3 ·5H 2 O (2) was partially characterized. In addition, three more dinuclear complexes [Cu 2 (H 2 L)(NO 3 ) 2 (H 2 O) 2 ](NO 3 ) 2 (3), [Cu 2 (HL)(OAc)(CH 3 OH)](PF 6 ) 2 (7) and [Cu 2 (HL)(NCS) 2 ]NO 3 ·2H 2 O (8) were also isolated. All complexes were characterized by CHN elemental analysis, IR and UV-Vis spectroscopy, ESI-MS, conductivity measurements and X-ray single crystal crystallography for compounds 1, 4, 5 and 6, where the bis(phenolato) ligand displayed different deprotonation (H 2 L, HL − and L 2− ). The magnetic susceptibility measurements over the temperature range 2–300 K revealed very weak antiferromagnetic coupling in dimanganese( ii ) 1 ( J = −1.64(1) cm −1 ) and almost negligible magnetic interaction in dicopper( ii ) 2 ( J = 0(3) cm −1 ). In the azido catena -[Cu 4 (HL) 2 (μ 1,1 -N 3 ) 2 (μ 1,3 -N 3 ) 2 ](NO 3 ) 2 ·5H 2 O (4) complex, the J value of −133(3) cm −1 was obtained upon moderate-to-strong antiferromagnetic coupling through the di-μ 1,3 -N 3 -bridged dicopper( ii ) unit with no magnetic interaction between the two copper( ii ) ions in the di-μ 1,1 -N 3 -bridged unit. 

   more » « less
3. Selective binding of anions by rigidified nanojars: sulfate vs. carbonate

   https://doi.org/10.1039/d1ob01318a  

   Al Isawi, Wisam A.; Salome, Austin Z.; Ahmed, Basil M.; Zeller, Matthias; Mezei, Gellert (September 2021, Organic & Biomolecular Chemistry)

   Selective binding and transport of highly hydrophilic anions is ubiquitous in nature, as anion binding proteins can differentiate between similar anions with over a million-fold efficiency. While comparable selectivity has occasionally been achieved for certain anions using small, artificial receptors, the selective binding of certain anions, such as sulfate in the presence of carbonate, remains a very challenging task. Nanojars of the formula [anion⊂{Cu(OH)(pz)} n ] 2− (pz = pyrazolate; n = 27–33) are totally selective for either CO 3 2− or SO 4 2− over anions such as NO 3 − , ClO 4 − , BF 4 − , Cl − , Br − and I − , but cannot differentiate between the two. We hypothesized that rigidification of the nanojar outer shell by tethering pairs of pyrazole moieties together will restrict the possible orientations of the OH hydrogen-bond donor groups in the anion-binding cavity of nanojars, similarly to anion-binding proteins, and will lead to selectivity. Indeed, by using either homoleptic or heteroleptic nanojars of the general formula [anion⊂Cu n (OH) n (L2–L6) y (pz) n −2 y ] 2− ( n = 26–31) based on a series of homologous ligands HpzCH 2 (CH 2 ) x CH 2 pzH ( x = 0–4; H 2 L2–H 2 L6), selectivity for carbonate (with L2 and with L4–L6/pz mixtures) or for sulfate (with L3) has been achieved. The synthesis of new ligands H 2 L3, H 2 L4 and H 2 L5, X-ray crystal structures of H 2 L4 and the tetrahydropyranyl-protected derivatives (THP) 2 L4 and (THP) 2 L5, synthesis and characterization by electrospray-ionization mass spectrometry (ESI-MS) of carbonate- and sulfate-nanojars derived from ligands H 2 L2–H 2 L6, as well as detailed selectivity studies for CO 3 2− vs. SO 4 2− using these novel nanojars are presented. 

   more » « less
4. 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. 

   more » « less
5. Back donation, intramolecular electron transfer and N–O bond scission targeting nitrogen oxyanion reduction: how can a metal complex assist?

   https://doi.org/10.1039/D0DT03430D  

   Beagan, Daniel M.; Cabelof, Alyssa C.; Caulton, Kenneth G. (February 2021, Dalton Transactions)

   null (Ed.)

   A density functional theory exploration studies a range of ancillary coordinated ligands accompanying nitrogen oxyanions with the goal of promoting back donation towards varied nitrogen oxidation states. Evaluation of a suite of Ru and Rh metal complexes reveals minimum back donation to the κ 1 -nitrogen oxyanion ligand, even upon one-electron reduction. This reveals some surprising consequences of reduction, including redox activity at pyridine and nitrogen oxyanion dissociation. Bidentate nitrate was therefore considered, where ancillary ligands enforce geometries that maximize M–NO x orbital overlap. This strategy is successful and leads to full electron transfer in several cases to form a pyramidal radical NO 3 2− ligand. The impact of ancillary ligand on degree of nitrate reduction is probed by comparing the powerful o-donor tris-carbene borate (TCB) to a milder donor, tris-pyrazolyl borate (Tp). This reveals that with the milder Tp donor, nitrate reduction is only seen upon addition of a Lewis base. Protonation of neutral and anionic (TCB)Ru(κ 2 -NO 3 ) at both terminal and internal oxygens reveals exergonic N–O bond cleavage for the reduced species, with one electron coming from Ru, yielding a Ru III hydroxide product. Comparison of H + to Na + electrophile shows weaker progress towards N–O bond scission. Finally, calculations on (TCB)Fe(κ 2 -NO 3 ) and [(TCB)Fe(κ 2 -NO 3 )] – show that electron transfer to nitrate is possible even with an earth abundant 3d metal. 

   more » « less