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3 Heterochemistry

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Lewis acidic silicon derivatives

Versatile Access to Martin’s Spirosilanes and Their Hypervalent Derivatives
H. Lenormand, V. Corcé, G. Sorin, C. Chuun, L.-M. Chamoreau, L. Krim, E.-L. Zins, J.-P. Goddard, L. Fensterbank J. Org. Chem. 2015, 15, DOI : 10.1021/jo5028497.

A new access to Martin’s spirosilanes has been devised. A series of derivatives bearing alkyl, aryl, halogen, alkoxy and trifluoromethyl substituents on the aryl ring have been prepared through a four step versatile route. Addition of fluoride onto these Lewis acids as a prototypical reaction with a nucleophile yielded a library of interesting stable fluorosilicates and both sets of compounds have been characterized by X-Ray crystallography.

Spirosilane Derivatives as Fluoride Sensors
H. Lenormand, J.-P. Goddard, L. Fensterbank Org. Lett. 2013, 15, 748-751.

A series of spirosilane derivatives have been investigated as potential fluoride sensors. The reactions between these compounds and different fluoride sources, yielding hypervalent derivatives, have been monitored and quantified by UV and fluorescence spectroscopy. The high selectivity of these probes for fluoride ions has been demonstrated in organic or aqueous media.

Study of Interaction between NO Radicals and Martin’s Spirosilane by Means of IR Spectroscopy
In collaboration with the Monaris Laboratory

Martin’ spirosilane 1 was reacted with NO in a neon matrix at 5 K. The generated species were characterized by in situ FT-IR spectroscopy in the 4000− 500 cm−1 region. This approach allowed us to characterize the NO adduct, leading to the formation of 1 -(NO). Concentration effects as well as annealing experiments were carried out. This stable species can further react with NO to form a more stable compound : 1 -(NO)2.Our results also proved that, in the dilute phase, the reaction between Martin’ spirosilane and NO radicals leads to the formation of an adduct. This study established the ability of spirosilane species to trap NO.

Bissulfoxides chemistry

Bis-Sulfoxides as Ligands for Platinum Complexes
Tetrahedron : Asymmetry 2010, 21, 1695-1700.

Two new platinum (II) complexes incorporating C2-symmetric enantiopure bis-sulfoxides ligands have been synthesiszed. The originality of these structures resides in the one-carbon tether between the two sulfoxides functions. X-ray structures show coordination takes place through both sulfur atoms giving birth to intriguing platina-cyclobutane systems. We anticipate that these complexes should find uses in asymmetric catalysis.

New Advances in Bis(sulfoxides) Chemistry Phosphorus, Sulfur, and Silicon 2003, 188, 367–376.
S. Beauvière, F. Brebion, S. Chelli, B. Delouvrié, C. Gomez, O. Kwasnieski, R. Martinez Mallorquin, F. Najera, G. Vincent, M. R. Vitale, E. Derat, I. Marek, M. Malacria, J.-P. Goddard, L. Fensterbank*

A short review describing all our results on the fascinating radical and polar reactivity of bis(sulfoxides) substrates.