TY - JOUR
T1 - An Isolable Mononuclear Palladium(I) Amido Complex
AU - Liu, Jian
AU - Bollmeyer, Melissa M.
AU - Kim, Yujeong
AU - Xiao, Dengmengfei
AU - Macmillan, Samantha N.
AU - Chen, Qi
AU - Leng, Xuebing
AU - Kim, Sun Hee
AU - Zhao, Lili
AU - Lancaster, Kyle M.
AU - Deng, Liang
N1 - Publisher Copyright:
© 2021 American Chemical Society. All rights reserved.
PY - 2021/7/21
Y1 - 2021/7/21
N2 - Mononuclear Pd(I) species are putative intermediates in Pd-catalyzed reactions, but our knowledge about them is limited due to difficulties in accessing them. Herein, we report the isolation of a Pd(I) amido complex, [(BINAP)Pd(NHArTrip)] (BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene, ArTrip = 2,6-bis(2′,4′,6′-triisopropylphenyl)phenyl), from the reaction of (BINAP)PdCl2 with LiNHArTrip. This Pd(I) amido species has been characterized by X-ray crystallography, electron paramagnetic resonance, and multiedge Pd X-ray absorption spectroscopy. Theoretical study revealed that, while the three-electron-two-center π-interaction between Pd and N in the Pd(I) complex imposes severe Pauli repulsion in its Pd-N bond, pronounced attractive interligand dispersion force aids its stabilization. In accord with its electronic features, reactions of homolytic Pd-N bond cleavage and deprotonation of primary amines are observed on the Pd(I) amido complex.
AB - Mononuclear Pd(I) species are putative intermediates in Pd-catalyzed reactions, but our knowledge about them is limited due to difficulties in accessing them. Herein, we report the isolation of a Pd(I) amido complex, [(BINAP)Pd(NHArTrip)] (BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene, ArTrip = 2,6-bis(2′,4′,6′-triisopropylphenyl)phenyl), from the reaction of (BINAP)PdCl2 with LiNHArTrip. This Pd(I) amido species has been characterized by X-ray crystallography, electron paramagnetic resonance, and multiedge Pd X-ray absorption spectroscopy. Theoretical study revealed that, while the three-electron-two-center π-interaction between Pd and N in the Pd(I) complex imposes severe Pauli repulsion in its Pd-N bond, pronounced attractive interligand dispersion force aids its stabilization. In accord with its electronic features, reactions of homolytic Pd-N bond cleavage and deprotonation of primary amines are observed on the Pd(I) amido complex.
UR - http://www.scopus.com/inward/record.url?scp=85111103884&partnerID=8YFLogxK
U2 - 10.1021/jacs.1c04965
DO - 10.1021/jacs.1c04965
M3 - 文章
C2 - 34232039
AN - SCOPUS:85111103884
SN - 0002-7863
VL - 143
SP - 10751
EP - 10759
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 28
ER -
