Synthesis and characterization of a RhNO complex with a PCN pincer ligand

JUAN PELLEGRINO; DAVID MILSTEIN; CECILIA M. GALLEGO; CARINA GAVIGLIO; YEHOSHOA BEN-DAVID; FABIO DOCTOROVICH

Puerto Iguazú

Simposio; SILQCOM6; 2017

Synthesis and characterization of a RhNO complex with a PCN pincer ligandC. M. Gallegoa, J. Pellegrinoa, C. Gaviglioa, Y. Ben-Davidb, D. Milsteinb, F. DoctorovichaaDQIAQF/INQUIMAE - CONICET, FCEN, UBA, CABA, Argentina.bDept. of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israelcgallego@qi.fcen.uba.arNitrosyl complexes are denoted {MNO}n, as proposed by Enemark and Feltham.1 In prior works, redox behaviour of {RhNO}8 with a PCP ligand and activation of carbon-halogen bonds by {RhNO}9 has been reported.2 In this work, we synthesized a {RhNO}8 complex with a PCN pincer ligand: [Rh(PCN)(NO)]+ (PHCN=N-[[3-(ditert-butylphosphanylmethyl)phenyl]methyl]-N-ethylethanamine), which is expected to be more readily oxidized and more labile, thus assisting C-X bond activation.{RhNO}8 was obtained by a four-step synthesis, where only the first step is reported[3]:PCHN + [Rh(COE)2Cl]2→Rh(PCN)(H)(Cl) [1]→Rh(PCN)N2 [2]→Rh(PCN)(NO)Cl [3]→[Rh(PCN)(NO)]+ [4]COE=CycloocteneProducts were characterized by 31P-NMR, 1H-NMR and film FTIR, where 4 showed a rapid decomposition when exposed to air which will be further studied. 1 and 3 were characterized by X-ray diffraction. Further studies of redox behaviour will be carried out.REFERENCES[1]Enemark, J. H.; Feltham, R. D. Coord. Chem. Rev. 1974, 13, 339.[2]Pellegrino. J.; Gaviglio, C.; Milstein, D.; Doctorovich, F. Organometallics. 2013, 32, 6555.[3]Cohen, R., Rybtchinski, B., Gandelman, M., et. al.J. Am. Chem. Soc., 2003, 125(21), 6532.