Polydentate Phosphane Ligands Featuring N, N, N'‐Trialkylformamidines. Issue 10 (12th February 2021)

• Record Type: Journal Article
• Authors: Marchenko, Anatoliy; Koidan, Georgyi; Hurieva, Anastasiya; Dyakonenko, Viktoriya V.; Shishkina, Svitlana V.; Rusanov, Eduard B.; Kyrylchuk, Andrii A.; Kostyuk, Aleksandr
• Is Part Of: European journal of inorganic chemistry. Issue 10(2021)
• Page Start: 969
• Page End: 981
• Publication Date: 2021-02-12
• Subjects: Phosphanes -- Reaction mechanisms -- Rearrangement -- Silylformamidine -- Structure elucidation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202001059
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: 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. Abstract : Novel N, N, N'‐trialkyl‐C‐silylformamidines were prepared. Their reactions with phosphorus (III) halides were studied. A set of polydentate phosphanes featuring one, two and three formamidine substituents was prepared. Chlorophosphanes featuring two formamidine substituents cyclized into diazaphospholium salts. A mechanism for their formation was proposed and corroborated by DFT calculations.