Synthesis, structure and properties of novel N-thiophosphorylated derivatives of 1,3-dihydro-2H-benzimidazol-2-imine and imidazolidine-2-imine

The reaction of bis-thiourea o-C₆H₄[NHC(S)NHP(S)(Oi-Pr)₂]₂ (1) with iodine, KOH and ClCH₂C(O)OCH₃ leads to O,O′-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylideneamidothiophosphate (2) formation. The complex of the potassium salt of compound 2 with 18-crown-6, having the composition [K(18-crown-6)L], has been synthesized. Bis-thiourea [CH₂NHC(S)NHP(S)(Oi-Pr)₂]₂ (6) forms a stable potassium salt, which oxidation by iodine leads to a product of heterocyclization, O,O′-diisopropyl-(1-{[(diisopropoxyphosphorothio)amino]carbonothioyl}imidazolidine-2-ylidene)amidothiophosphate (8), in which one of the thiourea fragments is kept.     

A “sodium trap” based on benzo-15-crown-5 with an exocyclic N-(thiophosphoryl)thiourea moiety

For N-(thio)phosphorylthioureas of the common formula RC(S)NHP(X)(OiPr)₂HL^I (R = N-(4′-aminobenzo-15-crown-5), X = S), HL^II (R = N-(4′-aminobenzo-15-crown-5), X = O), HL^III (R = PhNH, X = S), HL^IV (R = PhNH, X = O), and (N,N′-bis-[C(S)NHP(S)(OiPr)₂]₂-1,10-diaza-18-crown-6) H₂L^V, salts LiL^I,III,IV, NaL^I–IV, KL^I–IVM₂L^V (M = Li⁺, Na⁺, K⁺), Ba(L^I,III,IV)₂, and BaL^V have been synthesized and investigated. Compounds NaL^I,II quantitatively drop out as a deposit in ethanol medium, allowing the separation of Na⁺ and K⁺ cations. This effect is not displayed for the other compounds. The crystal structures of HL^III and the solvate of the composition [K(Me₂CO)L^III] have been investigated by X-ray crystallography.     

Erratum to: CONTENT OF THE ISSUE 2 (2022)

Journal of Structural Chemistry - An Erratum to this paper has been published: https://doi.org/10.1134/S0022476622040205     

Complexes of N-thiophosphorylthioureas (HL) with copper(I). Crystal structures of [Cu3L3] and [Cu(PPh3)2L] chelates

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RC(S)NHP(S)(OiPr)(2) [R = morpholin-N-yl (HL(a)), piperidin-N-yl (HL(b)), NH(2) (HL(c)), PhCH(2)NH (HL(d))] with Cu(PPh(3))(3)I in aqueous EtOH/CH(2)Cl(2) leads to mononuclear [Cu(PPh(3))(2)L-S,S'] complexes. Using copper(i) iodide instead of Cu(PPh(3))(3)I, polynuclear complexes [Cu(n)(L-S,S')(n)] were obtained. The structures of these compounds were investigated by ES-MS, elemental analyses, 1H and 31P NMR in solution, IR and 31P solid-state MAS NMR spectroscopy. The crystal structures of [Cu(3)L(3)(a)] and [Cu(PPh(3))(2)L(b)] were determined by single-crystal X-ray diffraction.     

Self-Assembly of the Complexes of Bipodal Thiophosphorylated Thioureas

N-Thiophosphorylated thioureas, of general formula [(i-PrO) 2 P(S)NHC(S)] 2 Z (Z = f , y -diamino(oxy)alkyl or 1,10-diaza-18-crown-6), in the form of potassium salts, react with a number of soft ions (Cd 2+ , Zn 2+ , Co 2+ , Ni 2+ , Pd 2+ ) to form novel dimeric complexes. The cadmium (Z = HN(CH 2 ) 2 NH), palladium (Z = HN(CH 2 ) 2 O(CH 2 ) 2 NH), and cobalt (Z = 1,10-diaza-18-crown-6) complexes were analyzed by x-ray crystallography. In the former complex, crown cavities remain free. This fact will allow us to obtain "guest-host" complexes with alkali metal cations.     

Complexes of N‐Thiophosphorylthiourea tBuNHC(S)NHP(S)(OiPr)2 with Zinc(II), Cadmium(II), Nickel(II), and Cobalt(II) Cations

Reaction of the potassium salt of N‐thiophosphorylthiourea tBuNHC(S)NHP(S)(OiPr)₂ ( HL ) with Zn^II, Cd^II, Ni^II and Co^II in aqueous EtOH leads to complexes of common formula M(L‐S,S′)₂ ( ML₂ ). Complexes were investigated by IR, UV‐Vis, ¹H and ³¹P{¹H} NMR spectroscopy and microanalysis The structure of complex NiL₂ was investigated by single crystal X‐ray diffraction analysis. The nickel(II) ion has a squre‐planar environment, S₄, with two anionic ligands involving 1,5‐S,S′‐coordination mode. The ligands are bound in a trans configuration.