Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Chen, Meng; Xu, Jingkai; Zhao, Deshi; Sun, Fangxiang; Tian, Songlin; Tu, Deshuang; Lu, Changsheng; Yan, Hong

doi:10.1002/ange.202205672

Cited by 3 publications

(7 citation statements)

References 155 publications

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“…261. 3441.52, 2956.78, 2927.38, 2615.89, 1402.17, 1311.35, 1176.90, 1098.79, 1002.91, 953.62, 906.70, 800.36, 734.89, 709.25 C,22.20;H,4.97;S,39.52;Found: C,22.23;H,4.89;S,39.58.…”

Section: Synthesis Of Ligandmentioning

confidence: 92%

“…Hence, 1 failed to characterize in solution, and its structure was confirmed through single-crystal X-ray diffraction. IR (KBr disk) ν: 3440.48, 3034,91, 2576.13, 1405.62, 1261.14, 1150.41, 1079.74, 1050.67, 952.87, 910.04, 800.81, 723,71, 562.64 2.68;S,12.27;Found: C,13.63;H,3.20;N,2.61;S,12.37.…”

Section: Synthesis Of Complexmentioning

confidence: 98%

“…-14.12, -13.35, -11.32, -10.50, -8.81, -7.95, -5.02, -3.45, -1.63, -0.38. IR (KBr disk) ν: 3440.42, 2984.57, 2569.84, 2213.59, 1400.93, 1372.88, 1233.35, 1198.88, 1147.39, 1113.46, 1076.84, 1054.63, 1012 11.35;Found: C,19.20;H,3.88;N,2.50;S,11.41.…”

Section: Synthesis Of Complexmentioning

confidence: 99%

“…-14.37, -13.31, -11.33, -7.96, -5.49, -3.37, -1.92, -1.08. IR (KBr disk) ν: 3440.20, 3004.26, 2953.87, 2585.35, 1404.77, 1246.49, 1149.09, 1078.72, 1052.26, 1009 C,16.86;H,3.71;S,16.88;Found: C,16.83;H,3.70;S,16.81.…”

Section: Synthesis Of Complexmentioning

confidence: 99%

“…Anal. calcd for 7 (m-C 2 B 10 H 9 (CS 2 CH 3 ) 2 (PdCl)): C,15.48;H,3.25;S,27.56;Found: C,15.54;H,3.26;S,27.67.…”

Section: Synthesis Of Complexmentioning

confidence: 99%

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Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane^†

et al. 2022

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Comprehensive Summary Herein, we describe the synthesis of a carborane‐supported octanuclear palladacycle complex, Pd8(o‐C2B10H10CS2CH3)4Cl4(CH3CN)4 (complex 1), with B(3)–H activations on o‐carborane ligand. The substitution reaction of 1 has been explored, and three of its substituted complexes Pd8(o‐C2B10H10CS2CH3)4Cl4(L)4 (L = tBuNC, 2; L = C5H5N, 3; L = C4H8S, 4) have been synthesized. The m‐ and p‐carborane disubstituted ligands m‐ and p‐C2B10H10(CS2CH3)2 (ligands 5 and 6) as well as their B—H activated carborane complexes [m‐C2B10H9(CS2CH3)2PdCl] (7) and [p‐C2B10H8(CS2CH3)2][PdCl(tBuNC)]2 (8) have also been synthesized by the similar method. All of these complexes have been characterized, including X‐ray single crystal diffraction, NMR spectroscopy, IR spectroscopy and elemental analysis methods.

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“…261. 3441.52, 2956.78, 2927.38, 2615.89, 1402.17, 1311.35, 1176.90, 1098.79, 1002.91, 953.62, 906.70, 800.36, 734.89, 709.25 C,22.20;H,4.97;S,39.52;Found: C,22.23;H,4.89;S,39.58.…”

Section: Synthesis Of Ligandmentioning

confidence: 92%

Section: Synthesis Of Complexmentioning

confidence: 98%

Section: Synthesis Of Complexmentioning

confidence: 99%

Section: Synthesis Of Complexmentioning

confidence: 99%

“…Anal. calcd for 7 (m-C 2 B 10 H 9 (CS 2 CH 3 ) 2 (PdCl)): C,15.48;H,3.25;S,27.56;Found: C,15.54;H,3.26;S,27.67.…”

Section: Synthesis Of Complexmentioning

confidence: 99%

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Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane^†

et al. 2022

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Persistent and Predominantly Localized Boron Radical from the Reduction of a Three‐Dimensional Analogue of NHC‐Stabilized Borafluorenium

Xiang

Wang

Krummenacher

et al. 2023

Chemistry A European J

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In this contribution, we reported the three-dimensional (3D) analogues of N-heterocyclic carbene (NHC)stabilized 9-borafluorenium and 9-borafluorene radical. The radical was fully characterized by cyclic voltammetry (CV), UV-Vis absorption spectroscopy, electron paramagnetic reso-nance (EPR) and single-crystal X-ray diffraction analyses. The distinct boron-centered radical character of 9-borafluorene radical was corroborated by DFT calculations and EPR analysis.

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Direct B–H Functionalization of Icosahedral Carboranes via Hydrogen Atom Transfer

Ren

Zhang

et al. 2023

J. Am. Chem. Soc.

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The efficient and selective functionalization of icosahedral carboranes (C 2 B 10 H 12 ) at the boron vertexes is a long-standing challenge owing to the presence of 10 inert B−H bonds in a similar chemical environment. Herein, we report a new reaction paradigm for direct B−H functionalization of icosahedral carboranes via B−H homolysis enabled by a nitrogen-centered radical-mediated hydrogen atom transfer (HAT) strategy. Both the HAT process of the carborane B−H bond and the resulting boroncentered carboranyl radical intermediate have been confirmed experimentally. The reaction occurs at the most electron-rich boron vertex with the lowest B−H bond dissociation energy (BDE). Using this strategy, diverse carborane derivatization, including thiolation, selenation, alkynylation, alkenylation, cyanation, and halogenation, have been achieved in satisfactory yields under a photoinitiated condition in a metal-free and redox-neutral fashion. Moreover, the synthetic utility of the current protocol was also demonstrated by both the scale-up reaction and the construction of carborane-based functional molecules. Therefore, this methodology opens a radical pathway to carborane functionalization, which is distinct from the B−H heterolytic mechanism in the traditional strategies.

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Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Cited by 3 publications

References 155 publications

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane^†

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane^†

Persistent and Predominantly Localized Boron Radical from the Reduction of a Three‐Dimensional Analogue of NHC‐Stabilized Borafluorenium

Direct B–H Functionalization of Icosahedral Carboranes via Hydrogen Atom Transfer

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Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Cited by 3 publications

References 155 publications

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane†

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane†

Persistent and Predominantly Localized Boron Radical from the Reduction of a Three‐Dimensional Analogue of NHC‐Stabilized Borafluorenium

Direct B–H Functionalization of Icosahedral Carboranes via Hydrogen Atom Transfer

Contact Info

Product

Resources

About

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane^†

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane^†