Dinuclear Nitrato Coordination Compounds with Bis(3,5‐tert‐butylpyrazol‐1‐yl)­acetate

Abstract

Two dinuclear centrosymmetric coordination compounds with the bis(3,5-di-tert-butylpyrazol-1-yl)acetic acid anion (L -= bdtbpza), namely, violet [Co(bdtbpza)(NO 3 )] 2 (1) and turquoise [Cu(bdtbpza)(NO 3 )] 2 (2), are reported. Around each metal(II) ion, the Lligand is κ 3 -N,N,O coordinated, and the M-O bonds are significantly longer than both M-N bonds. The coordination sphere is completed by short nitrato and M-O bonds to a ligand that is already κ 3 -N,N,O coordinated to the adjacent intra-dinuclear metal center. Therefore, each Lligand has a total coordination number of four but [a]

Syntheses and Biological Studies of Cu(II) Complexes Bearing Bis(pyrazol-1-yl)- and Bis(triazol-1-yl)-acetato Heteroscorpionate Ligands

“…Medium broad absorptions at 1705 and 1667 cm −1 , were observed in the spectrum of compound 1 , due to the carbonylic asymmetric stretching. They were shifted with respect to the same absorption observed for the free ligand of [HC(COOH)(pz Me2 ) 2 ] (1740 cm −1 ) and were in accordance with the presence of the uncoordinated protonated carboxylic group and coordinated to the metal center carboxylate ligand, respectively [34,47,48,50,58]. A broad absorption at 1736 cm −1 was present in the spectrum of compound 2 , due to the carbonylic asymmetric stretching of the COOH groups in the same range observed for the free ligand [HC(COOH)(pz) 2 ] (1722 cm −1 ).…”

“…Among them, complexes containing bis(pyrazol-1-yl)carboxylic acids are especially of interest, due to their κ 3 - N , N , O tripodal coordination behavior, as metalloenzyme models relevant for biochemistry [28,33,34,35,36,37,38,39,40,41,42] and as starting materials to yield bifunctional ligands [43,44,45,46]. In the nearly 15 years, the facially coordinating bis(pyazol-1-yl)acetate ligands, typically substituted at the 3,5-positions of the pyrazolyl rings, have been used to synthesize several structurally characterized copper(II) complexes [34,47,48,49,50,51,52,53,54,55,56,57,58]. Many of these coordination compounds were studied for their unique structural, electrochemical, and catalytic properties; however, to our knowledge, biological studies on the anticancer properties of bis(pyrazolyl)acetate copper(II) complexes are unknown.…”

Alkali‐Metal‐Templated Self‐Assembly of Nickel(II) [12‐MC‐3] Metallacoronates Based on Bis(pyrazol‐1‐yl)acetato Ligands

“…Tang also observed a two‐dimensional network [Cr(oxalato)(bdmpza)(H 2 O)] n , which is associated by hydrogen‐bonding involving a non‐coordinating oxygen donor of the oxalato ligand and the non‐coordinating oxygen donor of bdmpza with the H 2 O ligand of an adjacent molecule (Figure S2) . To the best of our knowledge, this is the first and sole example of a supramolecular system with bdmpza using all four potential coordination sites of the ligand (Figure ), although recently a κ 4 ‐ N , N , O,O′ coordination was also reported by B. Kozlevčar et al for the dinuclear complex [Cu(bd t bpza)(NO 3 )] 2 …”

“…As mentioned above, this coordination behaviour of bis(pyrazol‐1‐yl)acetato ligands has only been reported twice before. [19b], In other cases, such as the chromium network of Tang et al, a bridging interaction is not accomplished directly between the oxygen donor and another metal center but via hydrogen bridges to an H 2 O ligand of an adjoining complex unit.…”

Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(ii) derivative anchored with a ‘scorpionate’ precursor as a potential electrocatalyst for heterogeneous H2 evolution

“…codes BEDLAY, 17 CUMNOP, and CUMNUV. 18 BEDLAY and CUMNUV are a Fe(II) and a Co(II) complex, respectively; the coordination mode of bdtbpza is analogous to the one displayed in the title compound, but with chloride (BEDLAY) or nitrate (CUMNUV) instead of isothiocyanate as counter ions completing the coordination sphere of the metal, which has a distorted trigonal-bipyramidal geometry. In the case of CUPNOV, which is a copper coordination compound, the binding mode of bdtbpza is different, and involves both oxygen atoms of the acetate moiety bridging the two metal centers, yielding a square-pyramidal coordination completed by the nitrate anion acting as a monodentate ligand.…”