Ruchi Khajuria

Disubstituted diphenyldithiophosphates of cadmium: synthesis, characterization, and single-crystal X-ray structure

A series of new disubstituted diphenyldithiophosphate complexes of cadmium [{(ArO)2PS2}2Cd] (9–12) have been isolated in aqueous media while their donor stabilized adducts [{(ArO)2PS2}2Cd·2C5H5N] (13–16) [(Ar = 2,4-(CH3)2C6H3, 2,5-(CH3)2C6H3, 3,4-(CH3)2C6H3 and 3,5-(CH3)2C6H3)] have been isolated in chloroform. These newly synthesized complexes were characterized by elemental analyses, IR and NMR (1H, 13C and 31P) spectroscopic analyses. The dithiophosphate ligands are coordinated bidentate to the cadmium ion via the two thiolate sulfurs. The compounds [{(3,5-CH3)2C6H3O}2PS2HNEt3] (4) and [{(3,5-CH3)2C6H3O}2PS2]2Cd(NC5H5)2 (16) crystallize in the monoclinic system with space group P21/c. Single-crystal X-ray analysis of 4 reveals that phosphorus of the anion is tetrahedrally bonded to two S and two O atoms. The structure is stabilized by cation–anion N–H⋯S intermolecular hydrogen bond interactions. In 16, two diphenyldithiophosphate ions are bidentate with both sulfurs coordinated to cadmium. Each forms a four-membered chelate ring in the equatorial plane. Two pyridines are axially coordinated to cadmium leading to octahedral geometry. The thermal properties of this complex have also been examined by combined DTA/DTG thermal analyses. Graphical Abstract

Spectroscopic, Thermal, Electrochemical, and Antimicrobial Studies of Mononuclear Manganese(II) Ditolyldithiophosphates

New complexes of manganese(II) corresponding to [{(ArO)2PS2}2Mn] and [{(ArO)2PS2}2Mn.nL] (Ar = o-, m-, p-CH3C6H4 and p-Cl-m-CH3C6H3; n = 1, L = N2C12H8, N2C10H8; n = 2, L = NC5H5, P(C6H5)3) have been synthesized and characterized by microelemental analyses (C, H, and N), magnetic susceptibility, molar conductance, thermogravimetric, cyclic voltammetry, and spectral analyses including ESI mass spectrometry, IR, and UV-visible. The presence of a four-and-six coordinated Mn atoms has been established in the complexes and adducts, respectively. Antimicrobial screening of the complexes against gram negative bacteria E. coli, K. pneumonia, and P. aeruginosa and fungus S. rolfsii has shown potential bioactivity.

Iron(II) and iron(III) complexes of 3,5-dimethyl diphenyldithiophosphate: synthesis, characterization and single-crystal X-ray analysis

Abstract3,5-Dimethyl diphenyldithiophosphate complexes of Fe(II) and Fe(III), formulated as [{(3,5-(CH3)2C6H3O)2PS2}2Fe{NC5H4(C2H5)-4}2] (1) and [{(3,5-(CH3)2C6H3O)2PS2}3Fe] (2), have been synthesized and characterized by physicochemical, spectroscopic and single-crystal X-ray analysis. The crystal structure of complex 1 reveals mononuclear units with the Fe(II) center chelated in bidentate fashion by four S atoms of the two diphenyldithiophosphate ligands. The N atoms from two donor ligands are axially coordinated, leading to octahedral geometry around Fe(II). In complex 2, the coordination around the Fe(III) atom is best described as distorted octahedral, formed by six S atoms from the three chelating diphenyldithiophosphate ligands. The main core of the system is comprised of four-membered (FeS2P)3 heteroatomic rings and Fe(III) centers.

Synthesis and structural characterization of donor-stabilized disubstituted diphenyldithiophosphates of nickel(II)

Donor-stabilized addition complexes of nickel(II) with disubstituted diphenyldithiophosphates, [{(ArO)2PS2}2NiL2] {Ar = 2,4-(CH3)2C6H3 [(1), (5)], 2,5-(CH3)2C6H3 [(2), (6)], 3,4-(CH3)2C6H3 [(3), (7)] and 3,5-(CH3)2C6H3 [(4), (8)]; L = C5H5N [(1)-(4)] and C7H9N [(5)-(8)]}, were successfully isolated and characterized by elemental analysis, magnetic moment, IR spectroscopy and single-crystal X-ray analysis. Compound (4) crystallizes in the monoclinic space group P2(1)/n whereas compounds (7) and (8) crystallize in the triclinic space group P1. The single-crystal X-ray diffraction analysis of (4), (7) and (8) reveals a six-coordinated octahedral geometry for the NiS4N2 chromophore. Two diphenyldithiophosphate ions act as bidentate ligands with their S atoms coordinated to the Ni centre. Each of them forms a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Ni atom.

Triethylammonium salt of dimethyl diphenyldithiophosphates: Single crystal X-ray and DFT analysis

AbstractThe present work demonstrates the single crystal X-ray and DFT analysis of [{(2,4-CH3)2C6H3O}2 PS2HNEt3] (1) and [{(3,4-CH3)2C6H3O}2PS2HNEt3] (2) along with computational analysis of [{(3,5-CH3)2 C6H3O}2PS2HNEt3] (3) by using density functional theory (DFT) in its hybrid form B3LYP method. Compounds 1 and 2 crystallize in the orthorhombic space group Pbca and triclinic space group P1, respectively and their X-ray analysis reveals that phosphorus atom is coordinated to the two S and two O atoms to form tetrahedral geometry. The structure is stabilized by cation–anion N–H ⋯S hydrogen bonded interactions. The structural parameters, vibrational bands and energy gaps of frontier orbitals (HOMO–LUMO) have been calculated. The calculated geometric and spectral results matched the experimental data with good agreement. Theoretically calculated frontier molecular orbitals (HOMO–LUMO) and their energies suggest that charge transfer occurs within the compounds. Graphical AbstractDFT studies of the structural (geometries, bond lengths and bond angles) and spectroscopic properties (vibrational and HOMO–LUMO) of aromatic dithiophosphates are reported and compared with experimental results for the first time.

First Donor-Stabilized Complexes of Manganese(II) with Disubstituted diphenyldithiophosphates: synthesis, characterization, biological, and X-ray Analysis

GRAPHICAL ABSTRACT Abstract The complexes [{(ArO)2PS2}2Mn(NC5H5)2] (1–4) [(Ar = 2,4-(CH3)2C6H3 (1), 2,5-(CH3)2C6H3 (2), 3,4-(CH3)2C6H3 (3), and 3,5-(CH3)2C6H3) (4)] have been isolated in aqueous medium and characterized by mass spectrometer, IR, magnetic susceptibility, and single crystal X-ray analyses. The complex [{(2,4-(CH3)2C6H3O)2PS2)}2Mn(NC5H5)2] (1) crystallizes in the monoclinic space group P21/n as a monomer with a basic core of the four-membered ring [MnS4]. The octahedral sphere of the Mn atom is completed by donation from the nitrogen atoms of the two pyridine rings and four sulfur atoms of the dithio moiety. The thermal gravimetric analysis of the complex (1) revealed the end product as MnS. Screening of the ligands and complexes against the fungus Fusarium oxysporum has indicated potential antifungal activity.

Synthesis and structural elucidation of new complexes of 2,4‐ and 3,5‐dimethyl diphenyldithiophosphates with cobalt(II)

A new series of donor-stabilized addition complexes of cobalt(II) with disubstituted diphenyldithiophosphates [{(ArO)2PS2}2CoL2] {Ar = 2,4-(CH3)2C6H3 [(1)-(3)] and 3,5-(CH3)2C6H3 [(4)-(6)]; L = C5H5N [(1), (4)], 3,4-(CH3)2C5H3N [(2), (5)] and 4-(C2H5)C5H4N [(3), (6)]} were successfully isolated and characterized by elemental analyses, magnetic moment measurements, IR and single-crystal X-ray analysis. Complexes (3), (4) and (5) crystallize in the monoclinic space groups P2(1)/n, P2(1)/n and P2(1)/c, respectively, whereas complex (6) crystallizes in the triclinic space group P1¯. X-ray diffraction analysis of complexes (3)-(6) reveals a six-coordinated distorted octahedral geometry for the CoS4N2 chromophore defined by two chelating diphenyldithiophosphate anions as well as two N-donor ligands. Two diphenyldithiophosphate ligands are coordinated to the cobalt ion as a bidentate ligand chelating via the two thiolate S atoms. Each of them forms a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Co atom in a mutually trans position.