Synthesis, Characterization, and Crystal Structures of Scorpionate Complexes with the Hydrotris[3‐(2′‐thienyl)pyrazol‐1‐yl]borate Ligand

Abstract

Six scorpionate complexes of group 10-12 metal elements (Cu I , Cu II , Zn II , and Cd II ) containing the anionic hydrotris[3-(2Ј-thienyl)pyrazol-1-yl]borate (Tp Tn ) ligand were prepared from the reaction of the thallium(I) salt of Tp Tn with the corresponding metal acceptors in chloroform solution. The air-and heat-stable complexes were characterized by analytical and spectroscopic methods (IR, conductivity, ESI-MS, 1 H NMR and 13 C NMR solution data) and structurally characterized by single-crystal X-ray studies. The Zn II complexes [Zn-(Tp Tn )X] (X = Cl or Br) contain a tripodal tridentate Tp Tn ligand, in which the tetrahedral metal environment is completed by a halide; in [Cd(Tp Tn ) 2 ], cadmium is found in an octahedral environment coordinated by two Tp Tn ligands. In [Cu(Tp Tn )(PPh 3 )]·CHCl 3 and [Cu(Tp Tn )(OC(O)CH 3 )], Tp Tn is also coordinated in the tripodal fashion, in which the copper environment is completed by a triphenylphosphine ligand in the former complex and by a symmetrically coordinated bi-[a]

Tris(pyrazolyl)borate Copper Hydroxide Complexes Featuring Tunable Intramolecular H-Bonding

“…A τ 5 analysis (τ 5 = 0, square pyramidal; τ 5 = 1, trigonal bipyramidal) reveals a slight distortion toward trigonal bipyramidal geometries (τ 5 = 0.56 and 0.62) for 5b and 5c respectively (Figure ). Both feature monodentate acetate coordination, unlike in a simple Tn TpCu–OAc complex that possesses a bidentate acetate ligand. Related TpCu–OAc complexes with an extra copper donor such as [ PhMe TpCu­( PhMe PzH)]­OAc and [ Ph TpCu­( Ph PzH)]­OAc also feature monodentate acetate ligands, indicating that the presence of an additional ligand disfavors bidentate acetate coordination.…”

“…A τ 5 analysis 47 (τ 5 = 0, square pyramidal; τ 5 = 1, trigonal bipyramidal) reveals a slight distortion toward trigonal bipyramidal geometries (τ 5 = 0.56 and 0.62) for 5b and 5c respectively (Figure 4). Both feature monodentate acetate coordination, unlike in a simple Tn TpCu−OAc 48 4), respectively. While these angles are below the idealized 120°for sp 2 carbon centers, other Cu centers coordinated to bidentate py Pz ligands similarly show modest strain.…”

Synthesis, Characterization and Assessment of the Antioxidant Activity of Cu(II), Zn(II) and Cd(II) Complexes Derived from Scorpionate Ligands

“…The presence of neutral pyrazole in this complex was denounced by the missing band characteristic of the stretching vibration of B−H bond, and by the appearance, instead, of a broad band at 3148 cm −1 due to the vibration of the pyrazolyl N−H bond. This relatively rare behavior was already observed with other scorpionate ligands in the presence of transition metal(II) or metal(III) ions [36][37][38][39][40][41][42][43], and it is due not only to the different acidity of the metal centers, but also by the degree of steric crowding around the boron center in the corresponding scorpionate ligands [44].…”

catena-Poly[[tetrakis(3,5-dimethyl-1H-pyrazole-κN 2)copper(II)]-μ2-sulfato-κ2 O:O′]: crystal structure and Hirshfeld surface analysis of a CuII coordination polymer

“…Moreover there are 23 hits for the Cu(C 3 N 2 ) 2 SO 4 moiety, where C 3 N 2 is the backbone of the pyrazole ring. Most similar to the title compound are two catena-[( 2 -sulfato)bis(3,5-dimethyl-1H-pyrazole)aquacopper(II)dihydrate] complexes: EHOMEU (Wang et al, 2010) and EHOMEU01 (Gogoi et al, 2019); FITCUI, a complex based on 2-thienyl-1H-pyrazole (Pettinari et al, 2014); ZZZALD01 a tetrakis(pyrazole)(sulfato-O)copper(II) monohydrate (Shen et al, 2004); two monohydrated tetrapyrazole sulfato copper(II) complexes: LUNDAB (Kumar et al, 2014) and LUNDAB01 (Zerguini et al, 2019).…”