N-Acylamidophosphinates: Structure, Properties and Complexation Towards Main Group Metal Cations

Abstract

N-Acylamidophosphinates RC(X)NHP(Y)R' 2 (NAAP) and their thioanalogues (X,Y= O, S; R = Alk, Ar, CCl 3 , Het, NR 2 2 , NR 2 R 3 ; R ' = Ar, OAlk, OAr, SAlk, NAlk 2 , NHAr) contain X, Y donor atoms and amide nitrogen, which are capable of taking in complexation with metal cations. An application of NAAP complexes in supramolecular chemistry has been investigated in the last decades. Developed synthetic methods allow us to obtain N-acylamidophosphinate ligands contained multiple chelating groups or a combination of several essentially various coordinating fragments in the molecule: chelating moiety C(X)NHP(Y) and a macrocycle. The latter ligands are capable of connecting ions simultaneously by the chelating sites, and by the "guest-host" mechanism using the macrocycle. The bibliography includes 104 references.Investigation of complexing properties of conjugated organophosphorous anions is an important issue of modern coordination and organoelement chemistry [1,2]. The application of NMR, IR and UV spectroscopic methods to study the structure and dynamic processes in solutions of such compounds allows to investigate the nature of the chemical bonds in the conjugated organophosphorous anions and opens the way for the creation of new types of selective complexing agents.N-Acylamidophosphates, N-acylamidophosphinates and their thioanalogues with common formula RC(X)NHP(Y)R`2 (NAAP) contain X, Y donor atoms and an amido nitrogen atom which can be involved in complexation (Scheme 1). In terms of reactivity NAAP are quite different from each other depending on the nature and combination of atoms X and Y in the molecule, as well as the nature of substituents of (thio)carbonyl and (thio)phosphoryl moieties. Scheme 1.

Synthesis, Characterisation and Luminescent Properties of Mixed‐Ligand Copper(I) Complexes Incorporating N‐Thiophosphorylated Thioureas and Phosphane Ligands

“…(Table 2) are in the range typical for N-thiophosphorylated thiourea derivatives. [14] The two NC(S)N moieties show significant planarity (Figure 2). The two chelate backbones C(S)NP(S) are in Figure 5.…”

“…[6,[13][14][15][16][17][18][19][20] Only one dinuclear heteroligand complex of Cu I with N-thiophosphoryl bis(thiourea), containing 1,10-diaza-18-crown-6, and PPh 3 (Scheme 1) has been described. [6] To the best of our knowledge there are no crystal structures of such types of complexes.…”

Tetraphenylphosphonium salts of N‐thiophosphorylated thiobenzamide, mono‐thioureas or bis‐thioureas

“…These anions are versatile ligands for the synthesis of transition metal complexes [1,4]. At the same time, they form salt-like compounds with alkali or earth alkaline metal cations [1], which might be suitable precursors for transition metal complexes.…”

“…These anions are versatile ligands for the synthesis of transition metal complexes [1,4]. At the same time, they form salt-like compounds with alkali or earth alkaline metal cations [1], which might be suitable precursors for transition metal complexes. However, so far only very few of these salt-like compounds have been isolated and characterized, e.g., there is only one crystal structure of a K + salt of a N-(thio)phosphorylthiourea in the literature ([K(Me 2 CO)PhNHC(S)NP(S)(OiPr) 2 ]) [5].…”

“…It is known that N-(thio)phosphorylated (thio)ureas and (thio)amides RC(X)NHP(Y)(OR ) 2 (X, Y = O, S) in aqueous alcohol medium are weak acids and easily deprotonated under the influence of bases [1][2][3]. The negative charge is delocalized in the X-C-N-P-Y backbone and can be described by …”