An Operationally Unsaturated Iridium-Pincer Complex That C–H Activates Methane and Ethane in the Crystalline Solid-State DOI Creative Commons
Matthew R. Gyton, M. Arif Sajjad,

Daniel J. Storm

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The known complex [Ir(tBu-PONOP)MeH][BArF4], 1[BArF4] [tBu-PONOP = κ3-2,6-(tBu2PO)2C5H3N); ArF 3,5-(CF3)2(C6H3); J. Am. Chem. Soc. 2009, 131, 8603], is a robust precursor for in crystallo single-crystal to (SC-SC) C–H activation of methane and ethane at 80 °C. This contrasts with the reported solution (CD2Cl2) behavior, where decomposes by loss. Crystalline accessed as single polymorph on gram scale. A neutron diffraction study locates hydride. 13C{1H} SSNMR experiments 1[BArF4], its isotopologue [Ir(tBu-PONOP)(CD3)D][BArF4], d4-1[BArF4], suggest rapid reversible endergonic reductive bond formation occurring access an Ir(I) σ-methane complex. Heating °C under high vacuum results loss intramolecular form cyclometalated [Ir(cyclo-tBu-PONOP′)H][BArF4], 2[BArF4], SC-SC reaction. reversible, addition CH4 or CD4 2[BArF4] equilibrium respectively. Complex thus operationally unsaturated source 14-electron [Ir(tBu-PONOP)][BArF4], III, that undergoes methane. Periodic DFT studies, alongside isotope labeling experiments, link 2[BArF4]/CH4 via elimination/oxidative pathway. N2 forms [Ir(tBu-PONOP)(κ1-N2)][BArF4], transformation. Reaction CO [Ir(tBu-PONOP)(CO)][BArF4] room temperature. Calculations reaction occurs associative process competitively through while only operates. atmosphere alkane dehydrogenation, SC–SC reaction, forming ∼1:1 mixture [Ir(tBu-PONOP)(η2-H2C═CH2)][BArF4], [Ir(tBu-PONOP)H2][BArF4].

Language: Английский

An Operationally Unsaturated Iridium-Pincer Complex That C–H Activates Methane and Ethane in the Crystalline Solid-State DOI Creative Commons
Matthew R. Gyton, M. Arif Sajjad,

Daniel J. Storm

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The known complex [Ir(tBu-PONOP)MeH][BArF4], 1[BArF4] [tBu-PONOP = κ3-2,6-(tBu2PO)2C5H3N); ArF 3,5-(CF3)2(C6H3); J. Am. Chem. Soc. 2009, 131, 8603], is a robust precursor for in crystallo single-crystal to (SC-SC) C–H activation of methane and ethane at 80 °C. This contrasts with the reported solution (CD2Cl2) behavior, where decomposes by loss. Crystalline accessed as single polymorph on gram scale. A neutron diffraction study locates hydride. 13C{1H} SSNMR experiments 1[BArF4], its isotopologue [Ir(tBu-PONOP)(CD3)D][BArF4], d4-1[BArF4], suggest rapid reversible endergonic reductive bond formation occurring access an Ir(I) σ-methane complex. Heating °C under high vacuum results loss intramolecular form cyclometalated [Ir(cyclo-tBu-PONOP′)H][BArF4], 2[BArF4], SC-SC reaction. reversible, addition CH4 or CD4 2[BArF4] equilibrium respectively. Complex thus operationally unsaturated source 14-electron [Ir(tBu-PONOP)][BArF4], III, that undergoes methane. Periodic DFT studies, alongside isotope labeling experiments, link 2[BArF4]/CH4 via elimination/oxidative pathway. N2 forms [Ir(tBu-PONOP)(κ1-N2)][BArF4], transformation. Reaction CO [Ir(tBu-PONOP)(CO)][BArF4] room temperature. Calculations reaction occurs associative process competitively through while only operates. atmosphere alkane dehydrogenation, SC–SC reaction, forming ∼1:1 mixture [Ir(tBu-PONOP)(η2-H2C═CH2)][BArF4], [Ir(tBu-PONOP)H2][BArF4].

Language: Английский

Citations

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