Optical properties, structural, and DFT studies of Pd(II) complexes with 1‐phenyl‐1H‐tetrazol‐5‐thiol, X‐ray crystal structure of [Pd(κ¹‐S‐ptt)₂(κ²‐dppe)] complex

Abstract

Seven tetrazole‐thione complexes, [Pd2(κ2‐ptt)4](1), trans‐[Pd(k1‐S‐ptt)2(PPh3)2] (2), trans‐[Pd(k1‐S‐ptt)2(SPPh3)2] (3), trans‐[Pd(k1‐S‐ptt)2(OPPh3)2] (4), [Pd(k1‐N‐ptt)2(k2‐dppe)] (5a), [Pd(k1‐S‐ptt)2(k2‐dppe)] (5b), [Pd(k1‐S‐ptt)2(k2‐dppeS2)] (6), and [Pd(k1‐S‐ptt)2(k2‐dppeO2)] (7), were prepared from 1‐phenyl‐1H‐tetrazole‐5‐thiol (Hptt), with substituted phosphines. These complexes were investigated by CHNS analysis; infrared (IR), nuclear magnetic resonance (NMR) (1H and 31P), and ultraviolet–visible (UV–Vis) spectroscopy; and single‐crystal X‐ray data for 5b. In Complex 1, the ptt− ligand adopted μ2‐ k‐N, k‐S bridging mode to afford a dimeric complex, whereas in Complexes 2–4, 6, and 7, the ptt− was covalently coordinated via sulfur atom of the thiol group as a solo product. In contrast, in Complex 5, the ptt− ligand was bonded in a monodentate fashion through a deprotonated tetrazole ring nitrogen atom in isomer 5a or via a thiolato sulfur atom in isomer 5b. These linkage isomers were clearly shown in the 31P‐{1H} NMR. To explain the adoption of the ligand binding modes in Complexes 5a and 5b, geometry optimization calculations were carried out on two isomers. Very small differences of all molecular parameters were found between 5a and 5b isomers. This confirms the reason for obtaining two isomers. Also, theoretical studies are made for all compounds, and excellent agreement is obtained with experimental data. The direct band gap (Eg) values are equal to 2.88, 2.85, and 2.45 eV for Complexes 1, 2, and 4, respectively, revealing a semiconductor nature. The inhibition activity of Complexes 1–3, 5, and 8 were evaluated versus the growth of four types of bacteria in vitro. The complexes showed a good activity compared with free ligand and a standard antibiotic.

Exploration of novel phenyl mercury tetrazole‐thione complexes: Characterization and investigating the impact of diamine ligands on enhanced hydrogen storage

“…The IR spectrum of the [PhHg(mtzS)] complex (Figure S15) displayed the disappearance (S‐H) vibration which showed in the spectrum of the free 5‐mercapto‐1‐methyltetrazole ligand (Figure S16) (appeared at 2607 cm −1 ), indicates to the deprotonated of the proton of the HmtzS ligand and formed an anion form (mtzS − ) and coordinates to the metal ion through the sulfur atom of the thiolate group 10‐14 . Also, the spectrum displayed a strong band 1572 cm −1 due to the ν(C=N) 10‐14 .…”

“…[10][11][12][13][14] Also, the spectrum displayed a strong band 1572 cm À1 due to the ν(C=N). [10][11][12][13][14] The IR spectra of the complexes (2-7) (Figures S17-S20) displayed new bands within (1431-1435 cm À1 ) and (505-511 cm À1 ) due to the ν(Ph-P) and ν(P-C) the of the phosphine ligands, indicating their participation in complex formation. 33,36 The IR spectra of the complexes ( 8) and ( 9) displayed new bands within 1560 and 1589 cm À1 assigned to the ν(C=N) of the Bipy and Phen ligands, respectively, indicating their participation in complex formation, this band was shifted to lower frequency compared with free ligands, indicated that the amine were bonded through the nitrogen atom of the amine ligand.…”

“…They can act as monodentate ligands, coordinating with the metal through a single nitrogen or sulfur atom, or they can act as bi-dentate ligands, coordinate with the metal through both the nitrogen and sulfur atoms or as poly-dentate through the nitrogen and sulfur. [11][12][13][14][15][16][17][18][19][20] Tetrazole-thione complexes have been investigated for their potential applications in areas such as catalysis, luminescence, magnetism, and biological activity. [13][14][15] Their unique structural and electronic properties make them promising candidates for various technological and biomedical applications.…”

Synthesis, characterization, antibacterial, anticancer, and density‐functional theory studies of nano‐metal (II) oxime complexes

“…In our previous work, we reported the synthesis of transition and nontransition metal complexes of heterocyclic ligands such as tetrazole, dithiocarbamate, and oxime. [10,[24][25][26][27][28] In the present work, we describe the prepared phenolic aldoxime complexes with different metal ions with the study of nanoproperties; in addition, we examined for anticancer and antibacterial activity. Interestingly, different substitutes and spacer groups in the structure of ligand confer different electronic (space configuration, electron density distribution, and spectral), geometric, and biological properties of their metal complexes, which can be observed when computational studies are performed.…”

Antimicrobial, computational, and molecular docking studies of Zn (II) and Pd (II) complexes derived from piperidine dithiocarbamate

“…In doing so, it forms a small bite angle (S-M-S), ranging from 65 to 80 being dependent upon the size of the ligand and metal ion (B); [7,9, (iii) bidentate bridging mode through the two sulfur atoms or through the one of the sulfur atom only (C); [26,37,[39][40][41] (iv) poly-dentate mode between three center or more (D). [28,37,[42][43][44] Metal complexes of dithiocarbamate present a wide range of applications in agricultural science, medicine as antibacterial, anti-fungal, and anti-inflammatory, industry, analytical, and organic chemistry. [1][2][3][4][5][6][7][8][9][10][11] In the present work, we describe the synthesis, characterization, and biological activity of Zn (II) and Pd (II) mixed ligand complexes of piperidine dithiocarbamate (PipDT) and amine ligands {2,2 0 -bipyridineine (Bipy), 1,10-phenanthroline (Phen), and 3-aminopyridine (3Apy)}, whereas the treatment of cis-[PdCl 2 (PPh 3 ) 2 ] with sodium benzisothiazolinate (Nabit) or sodium saccharinate (Nasac), followed by addition, sodium piperidine dithiocarbamate (NaPipDT) to give complexes of the type trans-…”