Synthesis of Phosphorus(V)-Stabilized Geminal Dianions. The Cases of Mixed P=X/P?BH3 (X = S, O) and P=S/SiMe3 Derivatives

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

doi:10.1021/om300954a

Journal articles

Synthesis of Phosphorus(V)-Stabilized Geminal Dianions. The Cases of Mixed P=X/P?BH3 (X = S, O) and P=S/SiMe3 Derivatives

Hadrien Heuclin ¹ Marie Fustier-Boutignon ¹ Samuel Ying-Fu Ho ^{1, 2} X. Le Goff ¹ Sophie Carenco ¹ Cheuk-Wai So ^{1, 2} Nicolas Mézailles ^{1, *}

* Corresponding author

1 DCPH - Laboratoire Hétéroéléments et Coordination

2 Nanyang Technological University, School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry

Abstract : The monodeprotonation of [CH2(PPh2→BH3)(PPh2═E)] (E = S (6), O (7)) afforded [CH(PPh2→BH3)(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)(PPh2═S)] (8) also resulted in the partial formation of [C(SiMe3)(PPh2═S)]2- (82-), whose structure was confirmed by X-ray crystallography. The rare monomeric Mg carbene compound [MgC(PPh2→BH3)(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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Journal articles

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Chemical Sciences / Coordination chemistry

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Submitted on : Wednesday, November 20, 2013 - 11:14:41 AM
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Synthesis of Phosphorus(V)-Stabilized Geminal Dianions. The Cases of Mixed P=X/P?BH3 (X = S, O) and P=S/SiMe3 Derivatives

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Synthesis of Phosphorus(V)-Stabilized Geminal Dianions. The Cases of Mixed P=X/P?BH3 (X = S, O) and P=S/SiMe3 Derivatives

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