Photo-Induced ortho-C-H Borylation of Arenes through in Situ Generation of Rhodium(II) Ate Complexes
Photoinduced in situ "oxidation"of half-sandwich metal complexes to "high-valent"cationic metal complexes has been used to accelerate catalytic reactions. Here, we report the unprecedented photoinduced in situ "reduction"of half-sandwich metal [Rh(III)] complexes to "low-valent"anionic metal [Rh(II)] ate complexes, which facilitate ligand exchange with electron-deficient elements (diboron). This strategy was realized by using a functionalized cyclopentadienyl (CpA3) Rh(III) catalyst we developed, which enabled the basic group-directed room temperature ortho-C-H borylation of arenes.
Araujo Dias, Ant?nio Junio,Nagashima, Yuki,Tanaka, Jin,Tanaka, Ken
supporting information
p. 11325 - 11331
(2021/08/03)
COMPOUNDS
A compound of formula (I), or a pharmaceutically acceptable salt thereof.
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Page/Page column 90
(2020/01/24)
X-ray structures, photophysical characterization, and computational analysis of geometrically constrained copper(I) -Phenanthroline complexes
A series of three geometrically constrained C2-symmetric Cu(I) mono-phenanthroline complexes were characterized by X-ray structural analysis, and their photophysical properties were investigated by absorption and emission spectroscopy. Visible light excitation yielded metal-to-ligand charge-transfer (MLCT) excited states with luminescence lifetimes up to 155 ns. Ultrafast ransient absorption spectroscopy provided further insights into the excited-state dynamics and suggests for all three complexes the formation of a phenanthroline radical anion. In agreement with electrochemical measurements, the data further indicate that coordinative rearrangements are involved in nonradiative deactivation of the excited states. According to time-dependent density functional theory calculations (B3LYP/6-31G**), the major MLCT transitions are polarized along the C2 axis of the complex and originate predominantly from the copper dxz orbital. The computational analysis identifies an excited-state manifold with a number of close-lying, potentially emissive triplet states and is in agreement with the multiexponential decay kinetics of the MLCT luminescence. The relationship between structural and photophysical data of the studied Cu(I) mono-phenanthroline complexes agrees well with current models describing the photophysics of the related Cu(I) bis-diimine complexes.
Cody, John,Dennisson, Jeanette,Gilmore, Joshua,VanDerveer, Donald G.,Henary, Maged M.,Gabrielli, Alan,Sherrill, C. David,Zhang, Yiyun,Pan, Chia-Pin,Burda, Clemens,Fahrni, Christoph J.
p. 4918 - 4929
(2008/10/08)
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