Add time:09/29/2019         Source:infona.pl

This review is concerned with the role of the N,N ,N -trimethylethylenediamine group as a substituent at phosphorus atoms in different coordination and/or oxidation numbers. A few examples for silicon are also presented.Intramolecular donor-acceptor interactions between the nitrogen atom of the dimethylamino group and Si or P as the central atom were first noted in some N,N ,N -trimethylethylenediamine-substituted fluorosilanes (LSiF 3 , PhSiF 2 L) and P(III)Cl systems, e.g. LPCl 2 and PhP(Cl)L (L =N ,N ,N -trimethylethylenediamine group). These observations gave rise to a more detailed study of the coordinating behavior, especially of further phosphorus compounds of different substitution pattern. Spontaneous intramolecular coordination with formation of salt-like products was observed, especially, for compounds in which a phosphorus-bonded halogen atom is available to dissociate as an anion. A dependence both on the nature of the halogen atom and on the nature of other ligands at P(III) [or P(V)] was noted and will be discussed. Through the action of Lewis acids, e.g. AlCl 3 of PF 5 , or in the reaction with tetraphenylborate as a non-coordinating anion, halide abstraction and consequent formation of the Me 2 N → P coordinative bond from acyclic N,N ,N -trimethylethylenediamine-substituted halophosphines or trimethylethylenediamine-substituted fluorophosphoranes could be induced. No such Me 2 N → P coordination took place during oxidation of N,N ,N -trimethylethylenediamine-substituted phosphorus(III) compounds with oxidizing agents, e.g. sulfur, selenium, o-quinones or hexafluoroacetone. Numerous oxidation reactions were conducted on intramolecularly stabilized phospholidin-1-ium salts. They furnished the expected oxidation/addition products. This was accompanied in some cases (depending on the nature of the substituents at P(III)) by a scission of the coordinative Me 2 N → P bond. The reaction of phospholidin-1-ium salts with phenyl azide, dimethyl sulfoxide and sulfur furnished phosphonic acid diamides and substituted λ 4 -phospholidin-1-ium salts, as well as substituted diazadiphosphetidines, as a result of the dimerization of P=N species. Intramolecular donor-acceptor interaction inN ,N ,N -trimethylethylenediamine-substituted fluorophosphoranes was only observed in the presence of the Lewis acid, phosphorus pentafluoride leading to the formation of hexafluorophosphate salts. The reaction of dialkylamino-substituted tetrafluorophosphoranes withN -trimethylsilyl-N,N ,N -trimethylethylenediamine took an unusual course. Instead of the expected P-F cleavage and formation of anN ,N ,N -trimethylethylenediamine-substituted dialkylaminotrifluorophosphorane, cyclic tetrafluorophosphates with a λ 6 P atom, and dialkylaminotrimethylsilane were formed. The reaction of phosphorus(III)-N,N ,N -trimethylethylenediamine compounds with transition metal compounds [Fe(0), Cr(0), Mo(0), Pt(II)] furnished mono-, di- or trisubstituted coordination compounds, depending on the nature of the metal. The P(III) ligand was bonded in some cases via P(III) only (as a monodentate ligand) and in other cases as a chelating ligand coordinated via P(III) and N.A variety of variable-temperature NMR experiments have examined the dynamic processes occurring at room temperature in solution, and X-ray single-crystal structure determinations have been conducted in many cases to characterize these new and unusual compounds.

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