Zwitterionic Phosphoranides as Intermediates in the Reaction of Phosphorus Tribromide with N,N‐Dimethyl‐N′‐arylformamidines

Marchenko, A. P.; Koidan, G. N.; Hurieva, Anastasia N.; Rozhenko, Alexander; Kostyuk, Alexander

doi:10.1002/hc.21283

Cited by 9 publications

(9 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…N,N ‐dimethyl‐ N ‐arylformamidines were shown to react with phosphorus tribromide affording cyclic zwitterionic phosphoranides. Further, the reaction with amines yielded C‐phosphorylated formamidines [8] . Other phosphorus halides do not enter into the reaction.…”

Section: Introductionmentioning

confidence: 98%

Polydentate Phosphane Ligands Featuring N,N,N’‐Trialkylformamidines

et al. 2021

View full text Add to dashboard Cite

A set of novel polydentate phosphanes featuring one, two and three formamidine substituents was prepared by the reaction of C‐trimethylsilyl N,N,N’‐trialkylformamidines with P(III) chlorides. Chloro‐ and dichlorophosphanes gave tertiary phosphanes. More sterically congested adamantyldichlorophosphane reacted only with the least sterically congested silylformamidine. With phosphorus trichloride, five‐membered heterocycles, namely 1,4,2‐diazaphosphol‐4‐ium chlorides were formed in most cases. A mechanism for the formation of diazaphospholes was proposed and corroborated by DFT calculations. A key chlorophosphane underwent 1,2‐phosphorus shift giving the corresponding carbene that readily cyclized into diazaphospholium salts. The key compounds were studied by X‐ray diffractometry. Analysis of molecular structures of 1,4,2‐diazaphosphol‐4‐ium chloride 13 c and 1H‐1,4,2‐diazaphosphole 14 c revealed that the N‐Cring bonds for the orthogonally oriented i‐propylamino groups are unusually short. Only in the case of N,N‐dimethyl‐N’‐isopropyltrimethylsilylformamidine, we managed to isolate trisphosphane, albeit in a low yield.

show abstract

Section: Introductionmentioning

confidence: 98%

Polydentate Phosphane Ligands Featuring N,N,N’‐Trialkylformamidines

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Its structure was established by X-ray diffraction analysis. Based on DFT calculations, the mechanism for formation of phosphoranide 3 has been suggested (Scheme 1) [6]. e final step of the proposed mechanism is the reaction of dibromophosphine 2 with N,N-dimethyl-N′-phenylformamidine.…”

Section: Introductionmentioning

confidence: 99%

“…e perspective view of the molecule 9 with 50% probability ellipsoids for non-H-atoms. e selected bond lengths (Å) and angles (°): Cl(1)-P(1) 2.2058(6), Cl(2)-P(1) 2.8509(6), P(1)-N(4) 1.6621(13), P(1)-C(1) 1.8501(15), N(1)-C(1) 1.313(2), N(2)-C(1) 1.3255(19), N(2)-C(10) 1.5135(18), N(3)-C(10) 1.4115(19), N(4)-C(10) 1.4624(19); N(4)P(1)C(1) 89.10(7), P(1)C(1)N(2) 110.67(11), C(1)N(2)C(10) 116.88(12), N(2)C(10)N(4) 103.16(11), P(1)N(4)C(1).119.37(10). e perspective view of the molecule 11 with 50% probability ellipsoids for non-H-atoms.…”

mentioning

confidence: 99%

Dichlorophosphoranides Stabilized by Formamidinium Substituents

Marchenko

Koidan

Hurieva

et al. 2020

Heteroatom Chemistry

Self Cite

View full text Add to dashboard Cite

Dichlorophosphoranides featuring N,N-dimethyl-N′-arylformamidine substituents were isolated as individual compounds. Dichlorophosphoranide 9 was prepared by the multicomponent reaction of C-trimethylsilyl-N,N-dimethyl-N′-phenylformamidine and N,N-dimethyl-N′-phenylformamidine with phosphorus trichloride. Its molecular structure derived from a single-crystal X-ray diffraction was compared to the analogous dibromophosphoranide prepared previously by us by the reaction of phosphorus tribromide with N,N-dimethyl-N′-phenylformamidine. It was shown that a chlorophosphine featuring two N,N-dimethyl-N′-mesitylformamidine substituents reacted with hydrogen chloride to form dichlorophosphoranide 11. Its molecular structure was also determined by X-ray analysis and compared with that of closely related dichlorophosphoranide C.

show abstract

“…In continuation of our work on the synthesis of C ‐phosphanylformamidines, we used C ‐silylformamidine derivatives in the reaction with phosphorus(III) chlorides to introduce one, two, and three substituents to formamidine and prepare polydentate phosphane ligands. It should be noted that, with the exception of the most active phosphorus tribromide, the titled formamidines do not undergo a reaction with phosphorus halides …”

Section: Introductionmentioning

confidence: 99%

“…It should be noted that, with the exception of the most active phosphorus tribromide, the titled formamidines do not undergo a reaction with phosphorus halides. [18]…”

Section: Introductionmentioning

confidence: 99%

C‐Silyl‐N,N‐dialkyl‐N′‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

et al. 2016

View full text Add to dashboard Cite

A method for the synthesis of new C‐silyl‐N,N‐dialkyl‐N′‐arylformamidines was developed. These derivatives were formed by the deprotonation of N‐(trimethylsilyl)formamidinium salts to give the corresponding N‐trimethylsilyl carbenes followed by a 1,2‐migration of the silyl group. The reactions of C‐silylformamidines with phosphorus(III) chlorides were then studied. The reactions between chlorodiphenylphosphane and the C‐silylformamidines readily afforded C‐phosphanylformamidines in high yields. The reactions of dichlorophosphanes and C‐silylformamidines yielded previously unknown phosphanes that feature two formamidine substituents. In the reaction with phosphorus trichloride, the sterically least encumbered formamidine gave a stable two‐coordinate compound through the formation of an intermediate tris(phosphane). The reactions of the sterically more encumbered formamidines led to the substitution of only two chlorine atoms to give a chlorophosphane or benzazaphosphole. The structures of key compounds were proven by X‐ray crystal structure analyses.

show abstract

Zwitterionic Phosphoranides as Intermediates in the Reaction of Phosphorus Tribromide with N,N‐Dimethyl‐N′‐arylformamidines

Cited by 9 publications

References 31 publications

Polydentate Phosphane Ligands Featuring N,N,N’‐Trialkylformamidines

Polydentate Phosphane Ligands Featuring N,N,N’‐Trialkylformamidines

Dichlorophosphoranides Stabilized by Formamidinium Substituents

C‐Silyl‐N,N‐dialkyl‐N′‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

Contact Info

Product

Resources

About