Complexes of Crown Ether‐Containing N‐Phosphorylated Thioamides and Thioureas with Co^II, Zn^II and Pd^II Cations

Abstract

The reaction of the potassium salts of N‐phosphorylated thioureas [4′‐benzo‐15‐crown‐5]NHC(S)NHP(Y)(OiPr)2 (Y = S, HLI; Y = O, HLII) with ZnII and CoII cations in aqueous EtOH leads to complexes of formulae Zn(LI,II‐S,Y)2 (Y = S, 1; Y = O, 2) and Co(LI‐S,S′)2 (3), while interaction of the potassium salt of N‐phosphorylated thioamide [4′‐benzo‐15‐crown‐5]C(S)NHP(O)(OiPr)2 (HLIII) with ZnII in the same conditions leads to the complex Zn(HLIII)(LIII‐S,O)2 (4). The reaction of the potassium salt of crown ether‐containing N‐phosphorylated bis‐thiourea N,N′‐[C(S)NHP(O)(OiPr)2]2‐1,10‐diaza‐18‐crown‐6 (H2L) with CoII, ZnII and PdII cations in anhydrous CH3OH leads to complexes M2(L‐O,S)2 (M = Co, 5; Zn, 6; M = Pd, 7). Thioamide HLIII was investigated by single‐crystal X‐ray diffraction.

Synthesis and characterization of crown ether–containing N‐phosphorylated thioureas RC(S)NHP(O)(OiPr)2 (R = 1‐aza‐15‐crown‐5, 1‐aza‐12‐crown‐4) and their Co(II) and Ni(II) complexes

“…The derivatives of various crown ethers bearing one or two thioacylamido(thio)phosphate fragments C(S)NHP(X)(OR) 2 (X = O, S), their complexes with Co(II), Ni(II), Pd(II), Cu(I) and Cd(II) cations 10–17, and selective binding of sodium cations 18 were reported earlier by us. Ligands containing two essentially different complexing moieties, such as a chelating fragment and a macrocycle, possess the ability to form complexes with both alkaline and transition metal cations.…”

Pd[tBuNH(S)NHP(O)(OiPr)2-S]2Cl2 Complex as Air- and Moisture-Stable Catalyst for Palladium Catalyzed Suzuki Cross-Coupling Reaction

“…When H-bonding in the coordinated ligands RR 0 NC(S)NHP(O)(OiPr) 2 is not possible the deprotonation of them and a change of the coordination mode in the Pd(II) complexes occurs [31]. It was also Encouraged by our studies on the synthesis of palladium complexes with N-(thio)phosphoryl thioureas [31][32][33][34][35][36], and investigation of the catalytic properties of the Pd[N-MorphC(S)NP(O)(OiPr) 2 -1,5-O,S)] 2 complex in the Suzuki cross-coupling reaction [30], we decided to continue our investigations on the catalytic properties of new type of Pd(II) complexes.…”