Nouveaux complexes pinces POCOP, NHCCOP, PIMCOP et PIMIOCOP, et complexes cyclométallés de Ni(II) : synthèse, caractérisation et réactivité

Content Provider	Semantic Scholar
Author	Vabre, Boris
Copyright Year	2015
Abstract	This thesis describes the chemistry of Ni (II) pincer and cyclonickelated complexes bearing at least one phosphinite moiety. The content is divided into three parts. A first study concerns the synthesis, the characterization, the mechanism of formation and the reactivity of nickel complexes bearing a ligand POCOP (1,3-(iPr2PO)2C6H4). New ligands R-(POCOP) = κ P ,κ C ,κ P -{Rn-2,6-( R'2PO)2C6H3-n}; Rn = 4OMe, 4-Me, 4-CO2Me, 3-OMe, 3-CO2Me, 3,5-t-Bu2 ; R' = i-Pr, t-Bu have been synthesized by addition of chlorophosphine in presence of base in a resorcinol or derivatives solution. The synthesis of R-(POCOP)Ni(Br) complexes occurred by reacting the corresponding ligand in presence of base and{NiBr2(NC i Pr)}n. This new nickel precursor is synthesized in isobutyronitrile with bromine and metallic nickel powder. It is stable under inert atmosphere and its solubility in polar solvents allowed the study of those complexes in homogenous solution. Mechanism of formation of complexes bearing pincer ligands (PCsp3P) 1,3-(i-Pr2PCH2CH2)2CH2, (POCsp3OP) 1,3-(i-Pr2POCH2)2CH2, (PCsp2P) 1,3-(i-Pr2PCH2)2C6H4, Rn-(POCsp2OP) 1,3-(iPr2PO)2C6H4-n via C-H nickelation has been investigated by a method of competition reactions. The nickelation step was determined to be electrophilic. New {Rn-2,6-( R'2PO)2C6H4-n} ligands and corresponding nickel bromine complexes were characterized including linear correlation between 13 C NMR chemical shift of ipso carbon (Cipso) and oxidation potential Eox. A new greener methodology for the one pot synthesis of (POCOP)Ni(Cl) from metallic nickel has been developed. Reacting at 75 °C at mixture of resorcinol, chlorodiisopropylphosphine and nickel power gives (POCsp2OP)Ni(Cl) up to 93 %. Reactivity of this complex has been investigated for
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Language	English
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Resource Type	Article