Chemistry of iron complexes—III. X-ray diffraction,ESR and other spectral studies of new iron(II) and iron(III) complexes with tri-p-tolylarsine oxide

Reactions of iron(II) and iron(III) salts with tri-p-tolylarsine oxide(L) in suitable organic solvents yield complexes of formulas: (i) [FeL₂Cl₂(OH₂)₂] [FeCl₄].2H₂O, [FeL₂Br₂] [FeBr₄].2H₂O; (ii) [Fe(NCS)₃L₂].H₂O; (iii) [FeL(O₂ClO₂)₂(OH₂)] (ClO₄).0.25C₆H₆; (iv) [FeL₃I] [FeI₃].H₂O and (v) [Fe(CO)₃LI]I. Characterization has been done through elemental analyses, IR, far IR, ESR, and reflectance spectra, molar conductance, magnetic moments, t.g.a. and X-ray diffraction (powder) data. The species [FeL₂Cl₂(OH₂)₂]⁺, [FeL₂Br₂]⁺, [Fe(NCS)₃L₂], [FeL(O₂ClO₂)₂OH₂]⁺, [FeL₃I]⁺ and [Fe(CO)₃LI]⁺ have been assigned trans-octahedral, trans-square planar, trans-trigonal bipyramid, trans-octahedral, tetrahedral and cis-trigonal bipyramid structures respectively.     

A Sandmeyer type reaction for bromination of 2-mercapto-1-methyl-imidazoline (N2C4H6S) into 2-bromo-1-methyl-imidazole (N2C4H5Br) in presence of copper(I) bromide

2-Mercapto-1-methyl-imidazoline (N(2)C(4)H(6)S) is converted at room temperature into 2-bromo-1-methyl-imidazole (N(2)C(4)H(5)Br) in presence of copper(I) bromide in acetonitrile-chloroform mixture via extrusion of sulfur as sulfate and oxidation of Cu(I) into Cu(II). 2-Bromo-1-methyl-imidazole was isolated as its self assembled tetranuclear Cu(II) cluster, [Cu(4)(η(1)-N-(N(2)C(4)H(5)Br)(4)(μ(4)-O)(μ-Br)(6)] 1 {η(1)-N-(N(2)C(4)H(5)Br) = 2-bromo-1-methyl-imidazole}.     

Investigation of Silver(I) Ion Sensing Property of Ruthenium(II) Thiosemicarbazone Complex Using Coated Graphite and Polymeric Membrane Electrodes

A ruthenium(II) complex [Ru(PPh₃)₂(pytsc)₂] {Hpytsc = pyridine‐2‐carbaldehydethiosemicarbazone, (C₅H₅N)C²(H)=N³‐N²(H)‐C¹(=S)N¹H} has been used as an ion carrier for the selective determination of silver(I) ions in solution. Silver(I) ion‐selective coated graphite based (CGE) and PVC polymeric membrane based (PME) electrodes exhibit Nernstian slope for silver(I) ions over a wide concentration range from 1.0 × 10⁻¹ M to 5.0 × 10⁻⁶ M (with CGE) and 1.0 × 10⁻¹ M to 2.0 × 10⁻⁵ M (with PME). The working pH range of these electrodes has been found to be from 1.2 to 7.2 for CGE and 2.2 to 6.5 for PME. The proposed CGE sensor exhibits better analytical features like sensitivity and selectivity towards different secondary ions in comparison to the corresponding PME with no interference from mercury(II) ions . These electrodes also act as indicator electrodes in potentiometric titration and have been successfully used for the determination of silver content in solution of real samples (1 gm dissolved in 100 mL of dilute nitric acid) such as silver ornaments and thin silver foils. Silver content determined by the use of ion selective electrode was found to vary in the concentration range from 1.20 x 10⁻² M to 7.45 x 10⁻² M and results were found to be comparable with those obtained from the traditional volumetric method of analysis. It is the first report of a metal‐ligand complex used as an ion carrier in ion selective electrode, which is selective for a metal ion other than the one used in the complex.     

Variable Bonding Modes of Pyrimidine‐2‐thione in PdII/PtII Complexes [M(η2‐N,S‐pymS)(η1‐S‐pymS)(PPh3)] and [M(η1‐S‐pymS)2(L‐L)] (L‐L = dppm,dppe)

Reactions of pyrimidine‐2‐thione (HpymS) with Pd^II/Pt^IV salts in the presence of triphenyl phosphine and bis(diphenylphosphino)alkanes, Ph₂P‐(CH₂)_m‐PPh₂ (m = 1, 2) have yielded two types of complexes, viz. a) [M(η²‐N, S‐ pymS)(η¹‐S‐ pymS)(PPh₃)] (M = Pd, 1 ; Pt, 2 ), and (b) [M(η¹‐S‐pymS)₂(L‐L)] {L‐L, M = dppm (m = 1) Pd, 3 ; Pt, 4 ; dppe (m = 2), Pd, 5 ; Pt, 6 }. Complexes have been characterized by elemental analysis (C, H, N), NMR spectroscopy (¹H, ¹³C, ³¹P), and single crystal X‐ray crystallography ( 1 , 2 , 4 , and 5 ). Complexes 1 and 2 have terminal η¹‐S and chelating η²‐N, S‐modes of pymS⁻, while other Pd/Pt complexes have only terminal η¹‐S modes. The solution state ³¹P NMR spectral data reveal dynamic equilibrium for the complexes 3 , 5 and 6 , whereas the complexes 1 , 2 and 4 are static in solution state.     

Metal Derivatives of 1,3‐Imidazolidine‐2‐thione with Divalent d10 Metal Ions (Zn–Hg) : Synthesis and Structures

Reactions of divalent Zn‐Hg metal ions with 1,3‐imidazolidine‐2‐thione (imdtH₂) in 1 : 2 molar ratio have formed monomeric complexes, [Zn(η¹‐S‐imdtH₂)₂(OAc)₂] ( 1 ), [Cd((η¹‐SimdtH₂)₂I₂] ( 2 ), [Cd(η¹‐S‐imdtH₂)₂Br₂] ( 3 ), and [Hg(η¹‐S‐imdtH₂)₂I₂] ( 4 ). Complexes 1 – 4 , have been characterized by elemental analysis (C, H, N), spectroscopy (IR, ¹H, NMR) and x‐ray crystallography ( 1 ‐ 4 ). Hydrogen bonding between oxygen of acetate and imino hydrogen of ligand, {N(2)–H(2C)···O(2)^#} in 1 , ring CH and imino hydrogen, {C(2A)–H(2A)···Br(2)^#} in 3 have formed H‐bonded dimers. Similarly, the interactions between molecular units of complexes 2 and 4 have yielded 2D polymers. The polymerization occurs via intermolecular interactions between thione sulfur and imino hydrogen, {N(2)–H(2)···S(1)^#}, imino hydrogen and the iodine atom, {NH(1)···I(2)^#} in 2 and imino hydrogen – iodine atom {N(2A)–H(2A)···I(2)} and I···I interaction in 4 . Crystal data: [Zn(η¹‐S‐imdtH₂)₂(OAc)₂] ( 1 ), C₁₀H₁₈N₄O₄S₂Zn, orthorhombic, Pbcn, a = 9.3854(7) Å, b = 12.4647(10) Å, c = 13.2263(11) Å; V = 1547.3(2) ų, Z = 4, R = 0.0280 [Cd((η¹‐S‐imdtH₂)₂I₂] ( 2 ), C₆H₁₂CdI₂N₄S₂, orthorhombic, Pnma, a = 13.8487(10) Å, b = 14.4232(11) Å, c = 7.0659(5) Å; Z = 4, V = 1411.36(18) ų, R = 0.0186.     

Metal Derivatives of Thiosemicarbazones: Crystal and Mole­cular Structures of Mono‐ and Dinuclear Copper(II) Complexes with N1‐Subsitituted Salicylaldehyde Thiosemicarbazones

Reactions of copper(II) acetate with N¹‐subsitituted salicylaldehyde thiosemicarbazones [R¹R²C²=N³–N²H–C¹(=S)–N¹HR³;R¹ = 2‐HO–C₆H₄–, R² = H : R³ = Me (H₂L¹), Et (H₂L²)] are described. Copper(II) acetate was reacted with H₂L¹ and H₂L² ligands in the presence of polypyridyl co‐ligands, and this led to the formation ofmononuclear complexes, [Cu(κ³‐O, N, S‐L¹)(κ²‐N, N‐bipy)] ( 1 ),[Cu(κ³‐O, N, S‐L)(κ²‐N, N‐phen)] [L = L¹ ( 3 ), L² ( 4 )], [Cu(κ³‐O, N, S‐L)(κ²‐N, N‐tmphen)] [L =L¹ ( 5 ), L² ( 6 )] and a dinuclear complex, [Cu₂L²₂(bipy)] ( 2 ) (bipy = 2, 2′‐bipyridine, phen = 1, 10‐phenanthroline, tmphen = 3, 4, 7, 8‐tetramethyl‐1, 10‐phenanthroline). In dinuclear complex 2 , one ligand is O, N³,S‐chelating, while second is O, N³,S‐chelation‐cum‐N²‐bridging; and in all others thio‐ligands are O, N³,S‐chelating. The μ_eff values for the complexes lie in the range of 1.79–1.83 BM. Complexes 1 , 3 – 6 have square pyramidal arrangement, whereas complex 2 has two independent molecules in the crystal lattice, and each molecule has trigonal bipyramidal square planar (5:4) coordination pair. Complexes 2 , 4 , and 6 showed fluorescence properties.