Organometallics: Materials and Catalysis team

Abstract
This research PhD work deals with the functionalization and applications of the closo-decahydrido-decaborate cluster, through novel palladium mediated substitution and iron catalyzed reactions. In a first part, an efficient synthetic route for the preparation of phosphine substituted the closo-decahydrido-decaborate cluster by the substitution of apical iodine in [N(n C4H9)4]2[1 B10H9I] with tertiary phosphine ligands was selectively achieved in apical position, leading to the monoanionic cluster [N(nC4H9)4][1-B10H9PR3]. This reaction was promoted by Pd(0) phosphine complexes Pd(PR3)n (R = alkyl, aryl) at a mild temperature (50°C) with high yields up to 90%. These new phosphine borate clusters were fully characterized notably by X-ray crystal diffraction. This work provides an additional example of efficient synthetic routes for modifying closo-decahy-drido-decaborate clusters. In a second part, a series of original iron based complexes, [FeL₃][B₁₀H₁₀] were synthesized and fully cha-racterized starting from [NEt3H]2[B₁₀H₁₀] cluster FeX2 salts, and azoheterocyclic ligands [1,10-phenanthroline, 2,2’- bipyridydine, 4,7-dimethyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phen-anthroline, 5-nitro-1,10-phenanthroline, 5-ami-no-1,10-phenanthroline and 4,4-di-methyl-2,2-bipyridine. The catalytic properties of these complexes were then investigated, notably for the efficient homo-coupling of benzylamine derivatives leading to the corresponding imines. This result highlighted the crucial and efficient association iron/[B₁₀H₁₀]2- in catalytic transformations.

Jury

• Bohumir Gruner, Professor, Academy of Sciences, Prague, Czech Republic
• Richard Gil, Associate Professor, Université Paris Saclay, Orsay, France
• Nadine Pirio, Professor, Université de Bourgogne, Dijon, France
• Moutada Srour, Professor, Lebanese University, Lebanon
• Christophe Darcel Professor, ISCR, Université de Rennes, France / Thesis Supervisor
• Daoud Naoufal, Professor, Lebanese University, Lebanon / Thesis Co-Supervisor

Contact
Christophe Darcel (3 62 71) – christophe.darcel@univ-rennes.fr