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- W4286001207 abstract "The synthesis of P,N-phosphaalkene ligands, py-CH═PMes* (1, py = 2-pyridyl, Mes* = 2,4,6-tBu-C6H2) and the novel quin-CH═PMes* (2, quin = 2-quinolinyl) is described. The reaction with [Rh(μ-Cl)cod]2 produces Rh(I) bis(phosphaalkene) chlorido complexes 3 and 4 with distorted trigonal bipyramidal coordination environments. Complexes 3 and 4 show a pronounced metal-to-ligand charge transfer (MLCT) from Rh into the ligand P═C π* orbitals. Upon heating, quinoline-based complex 4 undergoes twofold C-H bond activation at the o-tBu groups of the Mes* substituents to yield the cationic bis(phosphaindane) Rh(I) complex 5, which could not be observed for the pyridine-based analogue 3. Using sub- or superstoichiometric amounts of AgOTf the C-H bond activation at an o-tBu group of one or at both Mes* was detected, respectively. Density functional theory (DFT) studies suggest an oxidative proton shift pathway as an alternative to a previously reported high-barrier oxidative addition at Rh(I). The Rh(I) mono- and bis(phosphaindane) triflate complexes 6 and 7, respectively, undergo deprotonation at the benzylic CH2 group of the phosphaindane unit in the presence of KOtBu to furnish neutral, distorted square-planar Rh(I) complexes 8 and 9, respectively, with one of the P,N ligands being dearomatized. All complexes were fully characterized, including multinuclear NMR, vibrational, and ultraviolet-visible (UV-vis) spectroscopy, as well as single-crystal X-ray and elemental analysis." @default.
- W4286001207 created "2022-07-21" @default.
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- W4286001207 date "2022-07-20" @default.
- W4286001207 modified "2023-09-27" @default.
- W4286001207 title "Synthesis, Coordination Chemistry, and Mechanistic Studies of P,N-Type Phosphaalkene-Based Rh(I) Complexes" @default.
- W4286001207 cites W1967722890 @default.
- W4286001207 cites W1969985642 @default.
- W4286001207 cites W1970437528 @default.
- W4286001207 cites W1979277497 @default.
- W4286001207 cites W1983316362 @default.
- W4286001207 cites W1984614201 @default.
- W4286001207 cites W1988057379 @default.
- W4286001207 cites W1988091937 @default.
- W4286001207 cites W1989099438 @default.
- W4286001207 cites W1998139531 @default.
- W4286001207 cites W2009359803 @default.
- W4286001207 cites W2022424476 @default.
- W4286001207 cites W2023271753 @default.
- W4286001207 cites W2023630158 @default.
- W4286001207 cites W2024680353 @default.
- W4286001207 cites W2030687437 @default.
- W4286001207 cites W2033383024 @default.
- W4286001207 cites W2035769965 @default.
- W4286001207 cites W2038533471 @default.
- W4286001207 cites W2041426400 @default.
- W4286001207 cites W2050592102 @default.
- W4286001207 cites W2051993011 @default.
- W4286001207 cites W2052796279 @default.
- W4286001207 cites W2071098422 @default.
- W4286001207 cites W2072066173 @default.
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- W4286001207 cites W2092157292 @default.
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- W4286001207 cites W2143981217 @default.
- W4286001207 cites W2165253538 @default.
- W4286001207 cites W2167722479 @default.
- W4286001207 cites W2171817715 @default.
- W4286001207 cites W2296493125 @default.
- W4286001207 cites W2301280296 @default.
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- W4286001207 cites W2332606781 @default.
- W4286001207 cites W2334107503 @default.
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- W4286001207 cites W2435693446 @default.
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- W4286001207 doi "https://doi.org/10.1021/acs.inorgchem.2c01158" @default.
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