Reactivity and mechanism of photo-and electrocatalytic hydrogen evolution by a diimine copper(I) complex

The tetrahedral copper(I) diimine complex [Cu(pq)2]BF4 displays high photocatalytic activity for the H2 evolution reaction with a turnover number of 3564, thus representing the first type of a Cu(I) quinoxaline complex capable of catalyzing proton reduction. Electrochemical experiments indicate that molecular mechanisms prevail and DFT calculations provide in-depth insight into the catalytic pathway, suggesting that the coordinating nitrogens play crucial roles in proton exchange and hydrogen formation. © 2020 by the authors. Licensee MDPI, Basel, Switzerland

Combining Azide, Carboxylate, and 2-Pyridyloximate Ligands in Transition-Metal Chemistry: Ferromagnetic Ni-5(II) Clusters with a Bowtie Skeleton

International audienceThe combined use of the anion of phenyl(2-pyridyl)ketone oxime (ppko(-)) and azides (N-3(-)) in nickel(II) carboxylate chemistry has afforded two new Ni-5(II) clusters, [Ni-5(O2CR')(2)(N-3)(4)(ppko)(4)(MeOH)(4)] [R' = H (1), Me (2)]. The structurally unprecedented {Ni-5(mu-N-3)(2)(mu(3)-N-3)(2)}(6+) cores of the two clusters are almost identical and contain the five Ni-II atoms in a bowtie topology. Two N-3(-) ions are end-on doubly bridging and the other two ions end-on triply bridging. The end-on mu(3)-N-3(-) groups link the central Ni-II atoms with the two peripheral metal ions on either side of the molecule, while the Ni center dot center dot center dot Ni bases of the triangles are each bridged by one end-on mu-N-3(-) group. Variable-temperature, solid-state direct(dc) and alternating-current (ac) magnetic susceptibility, and magnetization studies at 2.0 K were carried out on both complexes. The data indicate an overall ferromagnetic behavior and an S = 5 ground state for both compounds. The ac susceptibility studies on 1 reveal nonzero, frequency-dependent out-of-phase (chi(M)'') signals at temperatures below similar to 3:5 K; complex 2 reveals no chi(M)'' signals. However, single-crystal magnetization versus dc field scans at variable temperatures and variable sweep rates down to 0.04 K on 1 reveal no noticeable hysteresis loops, except very minor ones at 0.04 K assignable to weak intermolecular interactions propagated by nonclassical hydrogen bonds

Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn16 and Mn18 clusters

The employment of cyanato (OCN-) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)) and [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O2CMe)2·4H2O, hmpH, NaOCN and NEt3 in solvent MeOH or EtOH afford the isostructural complexes [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)). The [Mn16(μ4-O)4(μ3-O)4(μ-OMe)4(μ3-OR)6(μ-OR)6]10+ core of representative complex 1 comprises a MnII4MnIII4 double-cubane subunit attached on either side to two symmetry-related MnIIMnIII3 defective dicubanes. A similar reaction of Mn(O2CR)2·4H2O, hmpH, NaOCN and NEt3, but in solvent MeCN, led instead to the formation of [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [MnIII4(μ-O)6] rodlike subunit attached on either side to two symmetry-related [Mn7O9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear MnII/III complexes with structures different than these obtained from the use of the related azides

Investigation of the MSO4 · xH2O (M = Zn, x = 7; M = Cd, x = 8/3)/methyl 2-pyridyl ketone oxime reaction system: a novel Cd(II) coordination polymer versus mononuclear and dinuclear Zn(II) complexes

Summarization: The reactions of methyl 2-pyridyl ketone oxime, (py)C(Me)NOH, with MSO4 · xH2O (M = Zn, x = 7; M = Cd, x = 8/3), in the absence of an external base, have been investigated. The synthetic study has led to the two new complexes [Zn(SO4){(py)C(Me)NOH}(H2O)3] · H2O (1 · H2O) and [Zn2(SO4)2{(py)C(Me)NOH}4] · (py)C(Me)NOH [2 · (py)C(Me)NOH], and the coordination polymer [Cd(SO4){(py)C(Me)NOH}(H2O)]n · [Cd(SO4){(py)C(Me)NOH}(H2O)2]n (3). In the three complexes the organic ligand chelates through its nitrogen atoms. The sulfate anion in 1 · H2O is monodentate; the complex molecule is the mer isomer considering the positions of the aqua ligands. The ZnII centers in 2 · (py)C(Me)NOH are bridged by two syn, anti η1:η1:μ2View the MathML source ligands; each metal ion has the cis–cis–trans disposition of the coordinated sulfate oxygen, pyridyl nitrogen and oxime nitrogens, respectively. The molecular structure of 3 is unique consisting of two different linear and ladder – type chains. π–π stacking interactions and/or hydrogen bonds lead to the formation of interesting supramolecular architectures in the three complexes. The thermal decomposition of complex 3 has been studied. Characteristic vibrational (IR, Raman) bands are discussed in terms of the nature of bonding and the structures of the three complexes.Presented on: Inorganica Chimica Act