Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L 2 PhB: (L = Oxazol-2-ylidene)
The reactivity of L2PhB: (1; L = oxazol-2-ylidene) as well as its transition-metal (chromium and iron) complexes toward main-group substrates have been systematically examined, which led to the construction of B–E (E = C, Ga, Cl, H, F, N) bonds. The combination of 1 and triethylborane smoothly captu...
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| Format: | Journal Article |
| Language: | English |
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2017
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| Online Access: | https://hdl.handle.net/10356/85145 http://hdl.handle.net/10220/43662 |
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| author | Kong, Lingbing Lu, Wei Yongxin, Li Ganguly, Rakesh Kinjo, Rei |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Kong, Lingbing Lu, Wei Yongxin, Li Ganguly, Rakesh Kinjo, Rei |
| author_sort | Kong, Lingbing |
| collection | NTU |
| description | The reactivity of L2PhB: (1; L = oxazol-2-ylidene) as well as its transition-metal (chromium and iron) complexes toward main-group substrates have been systematically examined, which led to the construction of B–E (E = C, Ga, Cl, H, F, N) bonds. The combination of 1 and triethylborane smoothly captured carbon dioxide concomitant with the formation of B–C and B–O bonds. The soft basic boron center in 1 readily reacted with soft acidic gallium trichloride (GaCl3) to afford the extremely stable adduct 4 involving a B–Ga dative bond. Electrophilic alkylation of a neutral tricoordinate organoboron was first achieved by the treatment of 1 with dichloromethane and methyl trifluoromethanesulfonate (MeOTf), both of which afforded ionic species featuring an additional B–C bond. Comparatively, redox reactions took place when halides of heavier elements such as germanium dichloride, dichlorophenylphosphine, and chlorodiphenylbismuth were employed as substrates, from which cationic species 7 bearing a B–Cl bond was obtained. In addition, reactions of metal complexes [2, Cr(1)(CO)5; 8, Fe(1)(CO)4] with cationic electrophiles were investigated. With HOTf and FN(SO2Ph)2, the corresponding ionic species featuring a B–H bond (9) and a B–F bond (10) were formed via a formal electrophilic substitution reaction, whereas the reaction of 1 with F·Py-BF4 resulted in the formation of a dicationic boron species 11 with a newly formed B–N bond. |
| first_indexed | 2024-10-01T03:00:21Z |
| format | Journal Article |
| id | ntu-10356/85145 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:00:21Z |
| publishDate | 2017 |
| record_format | dspace |
| spelling | ntu-10356/851452023-02-28T19:31:38Z Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L 2 PhB: (L = Oxazol-2-ylidene) Kong, Lingbing Lu, Wei Yongxin, Li Ganguly, Rakesh Kinjo, Rei School of Physical and Mathematical Sciences New bond formation Boron Nucleophile The reactivity of L2PhB: (1; L = oxazol-2-ylidene) as well as its transition-metal (chromium and iron) complexes toward main-group substrates have been systematically examined, which led to the construction of B–E (E = C, Ga, Cl, H, F, N) bonds. The combination of 1 and triethylborane smoothly captured carbon dioxide concomitant with the formation of B–C and B–O bonds. The soft basic boron center in 1 readily reacted with soft acidic gallium trichloride (GaCl3) to afford the extremely stable adduct 4 involving a B–Ga dative bond. Electrophilic alkylation of a neutral tricoordinate organoboron was first achieved by the treatment of 1 with dichloromethane and methyl trifluoromethanesulfonate (MeOTf), both of which afforded ionic species featuring an additional B–C bond. Comparatively, redox reactions took place when halides of heavier elements such as germanium dichloride, dichlorophenylphosphine, and chlorodiphenylbismuth were employed as substrates, from which cationic species 7 bearing a B–Cl bond was obtained. In addition, reactions of metal complexes [2, Cr(1)(CO)5; 8, Fe(1)(CO)4] with cationic electrophiles were investigated. With HOTf and FN(SO2Ph)2, the corresponding ionic species featuring a B–H bond (9) and a B–F bond (10) were formed via a formal electrophilic substitution reaction, whereas the reaction of 1 with F·Py-BF4 resulted in the formation of a dicationic boron species 11 with a newly formed B–N bond. MOE (Min. of Education, S’pore) Accepted version 2017-08-31T03:43:12Z 2019-12-06T15:58:03Z 2017-08-31T03:43:12Z 2019-12-06T15:58:03Z 2017 Journal Article Kong, L., Lu, W., Yongxin, L., Ganguly, R., & Kinjo, R. (2017). Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L2PhB: (L = Oxazol-2-ylidene). Inorganic Chemistry, 56(10), 5586-5593. 0020-1669 https://hdl.handle.net/10356/85145 http://hdl.handle.net/10220/43662 10.1021/acs.inorgchem.6b02993 en Inorganic Chemistry © 2017 American Chemical Society. This is the author created version of a work that has been peer reviewed and accepted for publication by Inorganic Chemistry, American Chemical Society. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1021/acs.inorgchem.6b02993]. 10 p. application/pdf |
| spellingShingle | New bond formation Boron Nucleophile Kong, Lingbing Lu, Wei Yongxin, Li Ganguly, Rakesh Kinjo, Rei Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L 2 PhB: (L = Oxazol-2-ylidene) |
| title | Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L
2
PhB: (L = Oxazol-2-ylidene) |
| title_full | Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L
2
PhB: (L = Oxazol-2-ylidene) |
| title_fullStr | Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L
2
PhB: (L = Oxazol-2-ylidene) |
| title_full_unstemmed | Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L
2
PhB: (L = Oxazol-2-ylidene) |
| title_short | Formation of Boron–Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L
2
PhB: (L = Oxazol-2-ylidene) |
| title_sort | formation of boron main group element bonds by reactions with a tricoordinate organoboron l 2 phb l oxazol 2 ylidene |
| topic | New bond formation Boron Nucleophile |
| url | https://hdl.handle.net/10356/85145 http://hdl.handle.net/10220/43662 |
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