Transition‐Metal‐Promoted Functionalization of Carboranes

Qiu, Zaozao; Xie, Zuowei

doi:10.1002/9781118742952.ch7

Cited by 1 publication

(1 citation statement)

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“…Specifically, the chemistry of o -carboranes has been extensively expanded to diverse areas, including organometallic chemistry, − materials science, , energy storage, optoelectronics, , medicine, and so forth. Therefore, the B–H and C–H functionalization of o -carboranes has attracted enormous interest, ,− such as borylation, − alkylation, , alkenylation, , alkynylation, arylation, , halogenation, , and so on. Consequently, a large number of carborane derivatives have been synthesized and successfully utilized in small-molecule activation, such as NH 3 , CO, H 2 O, H 2 , CO 2 , and so on.…”

Section: Introductionmentioning

confidence: 99%

Predicting Dinitrogen Activation by Carborane-Based Frustrated Lewis Pairs

2022

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Activation of atmospherically abundant dinitrogen (N 2 ) under mild conditions has been a great challenge in chemistry for decades because of the significantly strong NN triple bond. The traditional strategy of N 2 activation was mainly limited to metallic species until the ground-breaking achievement of N 2 activation by two-coordinated borylenes was achieved experimentally in 2018. On the other hand, carborane derivatives have attracted considerable interest for small-molecule activation. Still, the utilization of carborane derivatives in N 2 activation remains elusive. Here, we design four types of carborane-based frustrated Lewis pairs (FLPs) to probe their potential for N 2 activation by systematical density functional theory calculations. Interestingly, all these carborane-based FLPs are found to become favorable both kinetically and thermodynamically for activating N 2 with low reaction barriers (ranging from 13.0 to 25.8 kcal mol −1 ) and high exothermicity, with ΔG values ranging from −37.5 to −51.0 kcal mol −1 , indicating a high potential for metal-free N 2 activation under mild conditions. Our study opens an avenue to metal-free N 2 activation, highlighting the great importance of carborane derivatives in the field of N 2 activation.

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