Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes
Abstract Direct conversion of dinitrogen (N2) into N-containing compounds beyond ammonia under ambient conditions remains a longstanding challenge. Herein, we present a Lewis acid-promoted strategy for diverse nitrogen-element bonds formation from N2 using chromium dinitrogen complex [Cp*(I i Pr2Me2...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-55998-5 |
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| author | Zhu-Bao Yin Gao-Xiang Wang Xuechao Yan Junnian Wei Zhenfeng Xi |
| author_facet | Zhu-Bao Yin Gao-Xiang Wang Xuechao Yan Junnian Wei Zhenfeng Xi |
| author_sort | Zhu-Bao Yin |
| collection | DOAJ |
| description | Abstract Direct conversion of dinitrogen (N2) into N-containing compounds beyond ammonia under ambient conditions remains a longstanding challenge. Herein, we present a Lewis acid-promoted strategy for diverse nitrogen-element bonds formation from N2 using chromium dinitrogen complex [Cp*(I i Pr2Me2)Cr(N2)2]K (1). With the help of Lewis acids AlMe3 and BF3, we successfully trap a series of fleeting diazenido intermediates and synthesize value-added compounds containing N−B, N−Ge, and N−P bonds with 3 d metals, offering a method for isolating unstable intermediates. Furthermore, the formation of N−C bonds is realized under more accessible conditions that avoid undesired side reactions. DFT calculations reveal that Lewis acids enhance the participation of dinitrogen units in the frontier orbitals, thereby promoting electrophilic functionalization. Moreover, Lewis acid replacement and a base-induced end-on to side-on switch of [NNMe] unit in [(Cp*(I i Pr2Me2)CrNN(BEt3)(Me)] (8) are achieved. |
| format | Article |
| id | doaj-art-a1ced15144924931949ce0ed48602469 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a1ced15144924931949ce0ed486024692025-01-19T12:29:53ZengNature PortfolioNature Communications2041-17232025-01-011611810.1038/s41467-025-55998-5Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexesZhu-Bao Yin0Gao-Xiang Wang1Xuechao Yan2Junnian Wei3Zhenfeng Xi4Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking UniversityBeijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking UniversityAbstract Direct conversion of dinitrogen (N2) into N-containing compounds beyond ammonia under ambient conditions remains a longstanding challenge. Herein, we present a Lewis acid-promoted strategy for diverse nitrogen-element bonds formation from N2 using chromium dinitrogen complex [Cp*(I i Pr2Me2)Cr(N2)2]K (1). With the help of Lewis acids AlMe3 and BF3, we successfully trap a series of fleeting diazenido intermediates and synthesize value-added compounds containing N−B, N−Ge, and N−P bonds with 3 d metals, offering a method for isolating unstable intermediates. Furthermore, the formation of N−C bonds is realized under more accessible conditions that avoid undesired side reactions. DFT calculations reveal that Lewis acids enhance the participation of dinitrogen units in the frontier orbitals, thereby promoting electrophilic functionalization. Moreover, Lewis acid replacement and a base-induced end-on to side-on switch of [NNMe] unit in [(Cp*(I i Pr2Me2)CrNN(BEt3)(Me)] (8) are achieved.https://doi.org/10.1038/s41467-025-55998-5 |
| spellingShingle | Zhu-Bao Yin Gao-Xiang Wang Xuechao Yan Junnian Wei Zhenfeng Xi Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes Nature Communications |
| title | Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes |
| title_full | Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes |
| title_fullStr | Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes |
| title_full_unstemmed | Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes |
| title_short | Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes |
| title_sort | construction of n e bonds via lewis acid promoted functionalization of chromium dinitrogen complexes |
| url | https://doi.org/10.1038/s41467-025-55998-5 |
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