V. D. Romanenko

Interaction of λ3-aminoiminophosphines with tris(trimethylsilyl) methyl- and bis (trimethylsilyl) methyl-lithium: a new approach to the synthesis of aminomethylenephosphines

Abstract N,N-Bis(trimethylsilyl)aminoiminophosphines 1 react with (Me3Si)3CLi and (Me3Si)2CHLi to form the stable aminomethylenephosphines 3 via nucleophilic displacement at the dicoordinated phosphorus atom with subsequent C → N silyl migration. This reaction is a new synthetic route to N-trimethylsilyl functionalized aminomethylenephosphines. Proton, 13C and 31P nmr spectroscopic data for the compounds 3 are reported.

STRUCTURAL ISOMERIZATION OF P-(P′-TRIMETHYLSILYLPHOSPHINO)-METHYLENEPHOSPHINE TO DIPHOSPHENE: A NEW APPROACH TO THE SYNTHESIS OF UNSYMMETRICAL DIPHOSPHENES

Abstract The reactions of P-chloro-bis(trimethylsilyl)methylenephosphine 1 with LiP(SiMe3)Bu t , LiP(SiMe3)Ar and LiN(SiMe3)Ar (Ar = 2,4,6-Bu t 3C6H2) have been investigated. Depending upon the steric bulk of the phosphorus substituent in starting silylphosphine, the product was either P-(P′-trimethylsilylphosphino)methylenephosphine 3 or the structurally rearranged diphosphene 4. The latter conversion constitutes the first example of P-phosphinomethylenephosphine → diphosphene isomerization. The product of the reaction of 1 with LiN(SiMe3)Ar exists in the form P-amino-methylenephosphine 6.

A NEW ENANTIOSELECTIVE ASYMMETRIC SYNTHESIS OF TRI-CO-ORDINATE PHOSPHORUS COMPOUNDS FROM DI-CO-ORDINATE λ3-ARYL(ALKYL)IMINOPHOSPHINES

Abstract The reaction of di-co-ordinate λ3-aryl(alkyl)iminophosphines (1) with achiral alcohols in the presence of optically active tertiary amines has been found to proceed in an asymmetric way affording optically active O-alkyl amidophosphonites (2). N-(2,4,6-Tris-t-butylphenyl)amido-O-methyl-phenyl-phosphonite (2a) was obtained in this way with 55% ee and the absolute configuration (S) was chemically linked with (+)-(R)-O-methyl t-butanephosphonothioic acid.

Intramolecular donor-stabilized phosphanylium salts via λ3-Functionalized-iminophosphanes

Abstract λ3-Iminophosphanes, R-P=NAr ∗ ( Ar ∗ =2,4,6-tri-tBuC 6 H 2 ),containing intramolecularly coordinating substituents at the dicoordinate phosphorus atom (R=8-NMe2 C10H6 or 2-Ph2PCH2 C6H4 have been synthesized and used for generation of the isolable phosphanylium salts stabilized by a donor P→ P bond.

THE INTERACTION OF PHOSPHENIMIDOUS AMIDES AND PHOSPHENODIIMIDIC AMIDES WITH AMINES

Abstract Phosphenimidous amides 1 react with amines to give phosphonimidic diamides 3a-b or phosphorous triamides 3d-f respectively. The nature of the product depends on the substituent R (Me3Si or t-Bu) attached to the imidic nitrogen. The amide and imide forms of the compounds 3 are relatively stable and incapable of interconvertion under the conditions investigated. The reaction between phosphenodiimidic amides 2 and amines leads to phosphorimidic triamide 4. The influence of different factors on the reactions is described. The spectroscopic data of the compounds are discussed in relation to their structure.

Synthesis, Structures and Reactivities of Dicoordinated Phosphorus Compounds

Abstract The results of experimental investigations by the authors in the area of the chemistry of two–coordinate phosphorus compounds are discussed. Main attention is devoted to a consideration of the new methods for the synthesis of compounds with P=N, P=P, P=As, P=Sb bonds and their conversions.

P-functionalized phosphaalkenes and iminophosphines : new results

Abstract Synthesis, structures, spectroscopic data, and novel reactions of P-[bis(dialkylamino)methylene-amino]- and P-[bis(dialkylamino)methylenephosphino]-substituted phosphaalkenes, iminophosphines and phosphenium ions are discussed.

Low-Coordinate Arsenic Chemistry: Studies of Amino(iminoarsanes) Using UV Photoelectron Spectroscopy and Density Functional Theory

In this paper, we report the gas-phase characterization of two differently substituted amino(iminoarsanes), TmpAs=NSiMe3 and (SiMe2tBu)2NAs=N(SiMe2tBu), by coupling flash vacuum thermolysis (FVT) with UV photoelectron spectroscopy (PES). Quantum chemical calculations, using the DFT method (B3LYP) with the basis set 6-311G(d,p), have also been carried out on the R1As=NR2 unit with R1 = H, NH2, N(CH3)2, N(SiH3)2 and R2 = H, SiH3, in order to study the effect of substitution on the electronic properties and the thermodynamic stability of the As=N skeleton. Similarities with phosphorus analogues are also discussed.

The First Examples of Donor-Stabilized Phosphanetriyl-Phosphonium [RP2]+ Ions

Abstract Synthesis of the first donor-stabilized phosphanetriylphosphonium ion [Ar∗PP<-PPh3]+ via trifluoromethanesulfonic acid (TfOH) induced reaction of P-dialkylaminodiphosphenes, Ar∗P=PNR2 (Ar∗ = 2,4,6-tri-tert-butylphenyl) with triphenylphosphane has been described.

P-Functionalized λ3-Iminophosphines and Diphosphenes

Abstract The synthesis of P-functionalized iminophosphines and diphosphenes is discussed. The reactivity and the coordination chemistry of selected compounds have been explored.