The Elusive Palladium-Diazo Adduct Captured: Synthesis, Isolation and Structural Characterization of [(ArNHC-PPh2 )Pd(η2 -N2 C(Ph)CO2 Et)]

Silvia G Rull; Eleuterio Álvarez; Manuel R Fructos; Tomás R Belderrain; Pedro J Pérez

doi:10.1002/chem.201701362

The Elusive Palladium-Diazo Adduct Captured: Synthesis, Isolation and Structural Characterization of [(ArNHC-PPh₂ )Pd(η² -N₂ C(Ph)CO₂ Et)]

Chemistry. 2017 Jun 7;23(32):7667-7671. doi: 10.1002/chem.201701362. Epub 2017 May 16.

Authors

Silvia G Rull¹, Eleuterio Álvarez², Manuel R Fructos¹, Tomás R Belderrain¹, Pedro J Pérez¹

Affiliations

¹ Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, 21007-, Huelva, Spain.
² Instituto de Investigaciones Químicas Isla de la Cartuja, CSIC-Universidad de Sevilla, Avenida de Américo Vespucio 49, 41092, Sevilla, Spain.

PMID: 28407417
DOI: 10.1002/chem.201701362

Abstract

The first example of a diazo palladium adduct is reported. The complexes [(ArNHC-PPh₂ )M(η² -N₂ C(Ph)CO₂ Et)] (M=Ni, 3; M=Pd, 4; ArNHC-PPh₂ =3-(2,6-diisopropylphenyl)-1-[(diphenylphosphino)ethyl]imidazol-2-ylidene) were prepared by ligand exchange with styrene-coordinated precursors [(ArNHC-PPh₂ )M(styrene)] (M=Ni, 1; M=Pd, 2). Complex 4 was fully characterized, including X-ray analyses; this constitutes the first example of a diazo adduct compound with palladium, thereby closing the gap between Groups 8 and 10 regarding this type of compounds.

Keywords: carbene transfer; diazo ligands; nhc-phosphine ligand; palladium diazo adduct; palladium(0) complexes.