Aldehyde Complexes of Zinc Halides

Abstract

Aldehyde complexes of the zinc halides were obtained by treating ZnCl2, ZnBr2, and ZnI2 under anhydrous conditions with large excesses of benzaldehyde and various substituted benzaldehydes. Their constitutions were determined by a total of 12 X‐ray structure analyses. Three product types were found: ZnHal2(aldehyde)2 (A), [ZnHal2(aldehyde)]∞ (B), and [Zn(aldehyde)6] [Zn2Hal6] (C). All three dissolve readily in the corresponding aldehyde or in polar nonprotic solvents indicating the presence of solvated zinc species in solution.

Unveiling the NLO Potential of New Zn (II) Complex of 6‐Methylpyridine‐2‐Carboxaldehyde: Experimental/DFT Study on Spectral, Static, and Frequency‐Dependent Linear/Nonlinear Optical Parameters

“…This shift is consistent with the results of the Zn (II) complexes obtained in different coordination with similar ligands and metal ions [4]. In contrast, the aldehyde– ν CO band shifts towards lower wavenumbers by approximately 50 cm −1 in zinc complexes of straight aldehydes (see Figure 2) [2–4]. In this study, because the ν CO band in the Zn (II) complex was observed at a wavenumber of 40 cm −1 lower than the free ligand, it can be said that ZnO interactions are strong or moderate (in Figure 2).…”

“…These results appear to have a similar trend to our previously reported study [40]. In complex structures with varied coordination geometries, differing/similar metal ions affect the changes in n and χ (3) parameters, and in different coordination structures with identical coordination geometries, these parameters alter depending on metal ion exchange [40,47,68,69].…”

“…The corresponding bond lengths were calculated at 1.969/1.959 and 2.04/2.15 Å by using DFT/M06L level, respectively. Zn Cl bond lengths in the Zn (II) complex obtained in the distorted trigonal bipyramidal geometry obtained in this study are within the normal range when compared with tetrahedral zinc halide complexes of straight aldehydes [3,4], but shifts in Zn O distances are observed. This obviously has to do with the donor atoms or groups in the molecules working better to accommodate the electron acceptor properties of the zinc ions.…”

New Monomeric Cobalt(II) and Zinc(II) Complexes of a Mixed N,S(alkylthiolate) Ligand: Model Complexes of (His)(His)(Cys) Metalloprotein Active Sites

“…The PATH ligand in the bromide complexes [(PATH)M II Br] (M = Co, Zn) is coordinated in the expected tridentate fashion, and together with the Br - ligand forms well-separated monomeric complexes whose geometry is best described as a distorted tetrahedron. The Zn−Br distance of 2.3277(5) Å for 2 matches well with other Zn−Br distances of four-coordinate Zn II complexes with terminal bromide ligands. , Likewise, the Co II −Br distance of 2.3810(5) Å for 4 falls within the range of known Co II −Br bond lengths in tetrahedral Co II complexes. , The thiocyanate complexes [(PATH)M II NCS] (M = Co, Zn) exhibit the identical monomeric, pseudotetrahedral structures in which the NCS - ligand has replaced the Br - ligand in the open site. The thiocyanate ligands in 3 and 5 are coordinated through their nitrogen atoms at a distance of 1.961(3) Å for 3 and 1.9414(18) Å for 5 with a slightly bent M−N−C angle of 168° (173°) for 3 ( 5 ).…”

“…The PATH ligand in the bromide complexes [(PATH)M II Br] (M ) Co, Zn) is coordinated in the expected tridentate fashion, and together with the Brligand forms well-separated monomeric complexes whose geometry is best described as a distorted tetrahedron. The Zn-Br distance of 2.3277(5) Å for 2 matches well with other Zn-Br distances of four-coordinate Zn II complexes with terminal bromide ligands 32,33. Likewise, the Co II -Br distance of 2.3810(5) Å for 4 falls within the range of known Co II -Br bond lengths in tetrahedral Co II complexes 34,35.…”