Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
Geometrically flexible 9-borabicyclo[3.3.1]nonyl units within the secondary coordination sphere enable isolation of high-spin Fe( ii )-dihydrides stabilized by boron-hydride interactions and a rare example of an isolable S = 3/2 reduction product. The borane-capped Fe( ii )-dihydride: (1) rapidly de...
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| Veröffentlicht in: | Chemical science (Cambridge) 2019-06, Vol.1 (21), p.5539-5545 |
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| creator | Kiernicki, John J Shanahan, James P Zeller, Matthias Szymczak, Nathaniel K |
| description | Geometrically flexible 9-borabicyclo[3.3.1]nonyl units within the secondary coordination sphere enable isolation of high-spin Fe(
ii
)-dihydrides stabilized by boron-hydride interactions and a rare example of an isolable
S
= 3/2 reduction product. The borane-capped Fe(
ii
)-dihydride: (1) rapidly deprotonates E-H (E = N, O, P, S) bonds to afford borane-stabilized Fe adducts and (2) releases H
2
upon exposure to π-acids. The Lewis acids provide an avenue for redox-leveling in analogy to the near constant operating potential for N
2
reduction in nitrogenase.
Pendent borane Lewis acids provide an avenue for changing a ligand's field strength through acid/base interactions; this strategy was highlighted within a series of biologically-relevant high spin iron hydrides. |
| doi_str_mv | 10.1039/c9sc00561g |
| format | Article |
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ii
)-dihydrides stabilized by boron-hydride interactions and a rare example of an isolable
S
= 3/2 reduction product. The borane-capped Fe(
ii
)-dihydride: (1) rapidly deprotonates E-H (E = N, O, P, S) bonds to afford borane-stabilized Fe adducts and (2) releases H
2
upon exposure to π-acids. The Lewis acids provide an avenue for redox-leveling in analogy to the near constant operating potential for N
2
reduction in nitrogenase.
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ii
)-dihydrides stabilized by boron-hydride interactions and a rare example of an isolable
S
= 3/2 reduction product. The borane-capped Fe(
ii
)-dihydride: (1) rapidly deprotonates E-H (E = N, O, P, S) bonds to afford borane-stabilized Fe adducts and (2) releases H
2
upon exposure to π-acids. The Lewis acids provide an avenue for redox-leveling in analogy to the near constant operating potential for N
2
reduction in nitrogenase.
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ii
)-dihydrides stabilized by boron-hydride interactions and a rare example of an isolable
S
= 3/2 reduction product. The borane-capped Fe(
ii
)-dihydride: (1) rapidly deprotonates E-H (E = N, O, P, S) bonds to afford borane-stabilized Fe adducts and (2) releases H
2
upon exposure to π-acids. The Lewis acids provide an avenue for redox-leveling in analogy to the near constant operating potential for N
2
reduction in nitrogenase.
Pendent borane Lewis acids provide an avenue for changing a ligand's field strength through acid/base interactions; this strategy was highlighted within a series of biologically-relevant high spin iron hydrides.</abstract><cop>England</cop><pmid>31293738</pmid><doi>10.1039/c9sc00561g</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-1296-1445</orcidid><oa>free_for_read</oa></addata></record> |
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| source | DOAJ Directory of Open Access Journals; PubMed Central Open Access; EZB-FREE-00999 freely available EZB journals; PubMed Central |
| title | Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides |
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