Facile Synthesis of Unsolvated Alkali Metal Octahydrotriborate Salts MB 3 H 8 (M=K, Rb, and Cs), Mechanisms of Formation, and the Crystal Structure of KB 3 H 8

A facile synthesis of heavy alkali metal octahydrotriborates (MB H ; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the pure alkali metals with THF⋅BH , does not require the use of electron carriers or the addition of other reaction media such as mercury, silica gel, or iner...

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Published inAngewandte Chemie International Edition Vol. 58; no. 9; pp. 2720 - 2724
Main Authors Chen, Xi-Meng, Ma, Nana, Liu, Xin-Ran, Wei, Changgeng, Cui, Chong-Chao, Cao, Bu-La, Guo, Yanhui, Wang, Lai-Sheng, Gu, Qinfen, Chen, Xuenian
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Published Germany 25.02.2019
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Abstract A facile synthesis of heavy alkali metal octahydrotriborates (MB H ; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the pure alkali metals with THF⋅BH , does not require the use of electron carriers or the addition of other reaction media such as mercury, silica gel, or inert salts as for previous procedures, and delivers the desired products at room temperature in very high yields. However, no reactions were observed when pure Li or Na was used. The reaction mechanisms for the heavy alkali metals were investigated both experimentally and computationally. The low sublimation energies of K, Rb, and Cs were found to be key for initiation of the reactions. The syntheses can be carried out at room temperature because all of the elementary reaction steps have low energy barriers, whereas reactions of LiBH /NaBH with THF⋅BH have to be carried out under reflux. The high stability and solubility of KB H were examined, and a crystal structure thereof was obtained for the first time.
AbstractList A facile synthesis of heavy alkali metal octahydrotriborates (MB H ; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the pure alkali metals with THF⋅BH , does not require the use of electron carriers or the addition of other reaction media such as mercury, silica gel, or inert salts as for previous procedures, and delivers the desired products at room temperature in very high yields. However, no reactions were observed when pure Li or Na was used. The reaction mechanisms for the heavy alkali metals were investigated both experimentally and computationally. The low sublimation energies of K, Rb, and Cs were found to be key for initiation of the reactions. The syntheses can be carried out at room temperature because all of the elementary reaction steps have low energy barriers, whereas reactions of LiBH /NaBH with THF⋅BH have to be carried out under reflux. The high stability and solubility of KB H were examined, and a crystal structure thereof was obtained for the first time.
Abstract A facile synthesis of heavy alkali metal octahydrotriborates (MB 3 H 8 ; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the pure alkali metals with THF⋅BH 3 , does not require the use of electron carriers or the addition of other reaction media such as mercury, silica gel, or inert salts as for previous procedures, and delivers the desired products at room temperature in very high yields. However, no reactions were observed when pure Li or Na was used. The reaction mechanisms for the heavy alkali metals were investigated both experimentally and computationally. The low sublimation energies of K, Rb, and Cs were found to be key for initiation of the reactions. The syntheses can be carried out at room temperature because all of the elementary reaction steps have low energy barriers, whereas reactions of LiBH 4 /NaBH 4 with THF⋅BH 3 have to be carried out under reflux. The high stability and solubility of KB 3 H 8 were examined, and a crystal structure thereof was obtained for the first time.
Author Cui, Chong-Chao
Wang, Lai-Sheng
Cao, Bu-La
Guo, Yanhui
Wei, Changgeng
Gu, Qinfen
Ma, Nana
Liu, Xin-Ran
Chen, Xuenian
Chen, Xi-Meng
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  organization: Department of Materials Science, Fudan University, Shanghai, 200433, China
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  orcidid: 0000-0003-1816-5738
  surname: Wang
  fullname: Wang, Lai-Sheng
  organization: Department of Chemistry, Brown University, Providence, RI, 02912, USA
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  organization: Australian Synchrotron (ANSTO), 800 Blackburn Rd, Clayton, 3168, VIC, Australia
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  givenname: Xuenian
  orcidid: 0000-0001-9029-1777
  surname: Chen
  fullname: Chen, Xuenian
  organization: College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, Henan, 450001, China
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Keywords nucleophilicity
X-ray diffraction
reaction mechanisms
boron
alkali metals
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Snippet A facile synthesis of heavy alkali metal octahydrotriborates (MB H ; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the pure alkali...
Abstract A facile synthesis of heavy alkali metal octahydrotriborates (MB 3 H 8 ; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the...
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Title Facile Synthesis of Unsolvated Alkali Metal Octahydrotriborate Salts MB 3 H 8 (M=K, Rb, and Cs), Mechanisms of Formation, and the Crystal Structure of KB 3 H 8
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