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A Dimetalloxycarbene Bonding Mode and Reductive Coupling Mechanism for Oxalate Formation from CO 2

Abstract : We describe the stable and isolable dimetalloxycarbene [(TiX3)2(μ2‐CO2‐κ2C,O:κO′)] 5, where X=N‐(tert‐butyl)‐3,5‐dimethylanilide, which is stabilized by fluctuating μ2‐κ2C,O:κ1O′ coordination of the carbene carbon to both titanium centers of the dinuclear complex 5, as shown by variable‐temperature NMR studies. Quantum chemical calculations on the unmodified molecule indicated a higher energy of only +10.5 kJ mol−1 for the μ2‐κ1O:κ1O′ bonding mode of the free dimetalloxycarbene compared to the μ2‐κ2C,O:κ1O′ bonding mode of the masked dimetalloxycarbene. The parent cationic bridging formate complex [(TiX3)2(μ2‐OCHO‐κO:κO′)][B(C6F5)4], 4[B(C6F5)4], was simply deprotonated with the strong base K(N(SiMe3)2) to give 5. Complex 5 reacts smoothly with CO2 to generate the bridging oxalate complex [(TiX3)2(μ2‐C2O4‐κO:κO′′)], 6, in a CC bond formation reaction commonly anticipated for oxalate formation by reductive coupling of CO2 on low‐valent transition‐metal complexes.
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https://hal.insa-toulouse.fr/hal-01968885
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Submitted on : Thursday, January 3, 2019 - 2:15:31 PM
Last modification on : Tuesday, March 3, 2020 - 11:40:04 AM

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  • HAL Id : hal-01968885, version 1

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Albert Paparo, Jared Silvia, Christos Kefalidis, Thomas Spaniol, Laurent Maron, et al.. A Dimetalloxycarbene Bonding Mode and Reductive Coupling Mechanism for Oxalate Formation from CO 2. Angewandte Chemie International Edition, Wiley-VCH Verlag, 2015, 54 (31), pp.9115-9119. ⟨hal-01968885⟩

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