Synthesis of phosphorus(V)-stabilized geminal dianions. the cases of mixed P=X/PBH3 (X = S, O) and P=S/SiMe3 derivatives

Hadrien Heuclin; Marie Fustier-Boutignon; Samuel Ying Fu Ho; Xavier Frédéric Le Goff; Sophie Carenco; Cheuk Wai So; Nicolas Mézailles

doi:10.1021/om300954a

Synthesis of phosphorus(V)-stabilized geminal dianions. the cases of mixed P=X/PBH₃ (X = S, O) and P=S/SiMe₃ derivatives

Hadrien Heuclin, Marie Fustier-Boutignon, Samuel Ying Fu Ho, Xavier Frédéric Le Goff, Sophie Carenco, Cheuk Wai So^*, Nicolas Mézailles

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

30 Citations (Scopus)

Abstract

The monodeprotonation of [CH₂(PPh₂BH ₃)(PPh₂=E)] (E = S (6), O (7)) afforded [CH(PPh ₂BH₃)(PPh₂=E)]^- (E = S (6 ^-), O (7^-)), whose structures were confirmed by X-ray crystallography. The kinetics of the second deprotonation appeared to be crucial in efficient synthesis of the corresponding dianions. Thus, the double deprotonation of 6 only led to 6^2-; the analogous reaction with 7 was slower and resulted only in the partial formation of 7^2-. Double deprotonation of the compound [CH₂(SiMe₃)(PPh ₂=S)] (8) also resulted in the partial formation of [C(SiMe ₃)(PPh₂=S)]^2- (8^2-), whose structure was confirmed by X-ray crystallography. The rare monomeric Mg carbene compound [MgC(PPh₂BH₃)(PPh₂=S)] (9) was obtained by the reaction of 6 with Mg(nBu)₂. The X-ray structure of 9 is presented.

Original language	English
Pages (from-to)	498-508
Number of pages	11
Journal	Organometallics
Volume	32
Issue number	2
DOIs	https://doi.org/10.1021/om300954a
Publication status	Published - Jan 28 2013
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{380d1d4b9208419bb08b2584b3652092,

title = "Synthesis of phosphorus(V)-stabilized geminal dianions. the cases of mixed P=X/PBH3 (X = S, O) and P=S/SiMe3 derivatives",

abstract = "The monodeprotonation of [CH2(PPh2BH 3)(PPh2=E)] (E = S (6), O (7)) afforded [CH(PPh 2BH3)(PPh2=E)]- (E = S (6 -), O (7-)), whose structures were confirmed by X-ray crystallography. The kinetics of the second deprotonation appeared to be crucial in efficient synthesis of the corresponding dianions. Thus, the double deprotonation of 6 only led to 62-; the analogous reaction with 7 was slower and resulted only in the partial formation of 72-. Double deprotonation of the compound [CH2(SiMe3)(PPh 2=S)] (8) also resulted in the partial formation of [C(SiMe 3)(PPh2=S)]2- (82-), whose structure was confirmed by X-ray crystallography. The rare monomeric Mg carbene compound [MgC(PPh2BH3)(PPh2=S)] (9) was obtained by the reaction of 6 with Mg(nBu)2. The X-ray structure of 9 is presented.",

author = "Hadrien Heuclin and Marie Fustier-Boutignon and Ho, {Samuel Ying Fu} and Goff, {Xavier Fr{\'e}d{\'e}ric Le} and Sophie Carenco and So, {Cheuk Wai} and Nicolas M{\'e}zailles",

year = "2013",

month = jan,

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doi = "10.1021/om300954a",

language = "English",

volume = "32",

pages = "498--508",

journal = "Organometallics",

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T1 - Synthesis of phosphorus(V)-stabilized geminal dianions. the cases of mixed P=X/PBH3 (X = S, O) and P=S/SiMe3 derivatives

AU - Heuclin, Hadrien

AU - Fustier-Boutignon, Marie

AU - Ho, Samuel Ying Fu

AU - Goff, Xavier Frédéric Le

AU - Carenco, Sophie

AU - So, Cheuk Wai

AU - Mézailles, Nicolas

PY - 2013/1/28

Y1 - 2013/1/28

N2 - The monodeprotonation of [CH2(PPh2BH 3)(PPh2=E)] (E = S (6), O (7)) afforded [CH(PPh 2BH3)(PPh2=E)]- (E = S (6 -), O (7-)), whose structures were confirmed by X-ray crystallography. The kinetics of the second deprotonation appeared to be crucial in efficient synthesis of the corresponding dianions. Thus, the double deprotonation of 6 only led to 62-; the analogous reaction with 7 was slower and resulted only in the partial formation of 72-. Double deprotonation of the compound [CH2(SiMe3)(PPh 2=S)] (8) also resulted in the partial formation of [C(SiMe 3)(PPh2=S)]2- (82-), whose structure was confirmed by X-ray crystallography. The rare monomeric Mg carbene compound [MgC(PPh2BH3)(PPh2=S)] (9) was obtained by the reaction of 6 with Mg(nBu)2. The X-ray structure of 9 is presented.

AB - The monodeprotonation of [CH2(PPh2BH 3)(PPh2=E)] (E = S (6), O (7)) afforded [CH(PPh 2BH3)(PPh2=E)]- (E = S (6 -), O (7-)), whose structures were confirmed by X-ray crystallography. The kinetics of the second deprotonation appeared to be crucial in efficient synthesis of the corresponding dianions. Thus, the double deprotonation of 6 only led to 62-; the analogous reaction with 7 was slower and resulted only in the partial formation of 72-. Double deprotonation of the compound [CH2(SiMe3)(PPh 2=S)] (8) also resulted in the partial formation of [C(SiMe 3)(PPh2=S)]2- (82-), whose structure was confirmed by X-ray crystallography. The rare monomeric Mg carbene compound [MgC(PPh2BH3)(PPh2=S)] (9) was obtained by the reaction of 6 with Mg(nBu)2. The X-ray structure of 9 is presented.

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Synthesis of phosphorus(V)-stabilized geminal dianions. the cases of mixed P=X/PBH₃ (X = S, O) and P=S/SiMe₃ derivatives

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