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Catalytic Dinitrogen Reduction to Ammonia at a Triamidoamine–Titanium Complex
| Content Provider | Scilit |
|---|---|
| Author | Doyle, Laurence Wooles, Ashley Jenkins, Lucy C. Tuna, Floriana McInnes, Eric J. L. Liddle, Stephen T. |
| Copyright Year | 2018 |
| Description | Journal: Angewandte Chemie International Edition Catalytic reduction of $N_{2}$ to $NH_{3}$ by a Ti complex has been achieved, thus now adding an early d‐block metal to the small group of mid‐ and late‐d‐block metals (Mo, Fe, Ru, Os, Co) that catalytically produce $NH_{3}$ by $N_{2}$ reduction and protonolysis under homogeneous, abiological conditions. Reduction of $[Ti^{IV}(Tren^{TMS}$)X] (X=Cl, 1A; I, 1B; Tren^{TMS}$=N(CH_{2}CH_{2}NSiMe_{3})_{3}$) with $KC_{8}$ affords $[Ti^{III}(Tren^{TMS}$)] (2). Addition of $N_{2}$ affords [{(Tren^{TMS})Ti^{III}}_{2}(μ‐η^{1}:η^{1}$‐N_{2}$)] (3); further reduction with $KC_{8}$ gives [{(Tren^{TMS})Ti^{IV}}_{2}(μ‐η^{1}:η^{1}:η^{2}:η^{2}$‐N_{2}K_{2}$)] (4). Addition of benzo‐15‐crown‐5 ether (B15C5) to 4 affords [{(Tren^{TMS})Ti^{IV}}_{2}(μ‐η^{1}:η^{1}$‐N_{2})][K(B15C5)_{2}]_{2}$ (5). Complexes 3–5 treated under $N_{2}$ with $KC_{8}$ and $[R_{3}$PH][I], (the weakest $H^{+}$ source yet used in $N_{2}$ reduction) produce up to 18 equiv of $NH_{3}$ with only trace $N_{2}H_{4}$. When only acid is present, $N_{2}H_{4}$ is the dominant product, suggesting successive protonation produces [{(Tren^{TMS})Ti^{IV}}_{2}(μ‐η^{1}:η^{1}$‐N_{2}H_{4})][I]_{2}$, and that extruded $N_{2}H_{4}$ reacts further with $[R_{3}PH][I]/KC_{8}$ to form $NH_{3}$. |
| Related Links | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6003280/pdf |
| Ending Page | 6318 |
| Page Count | 5 |
| Starting Page | 6314 |
| ISSN | 14337851 |
| e-ISSN | 15213773 |
| DOI | 10.1002/anie.201802576 |
| Journal | Angewandte Chemie International Edition |
| Issue Number | 21 |
| Volume Number | 57 |
| Language | English |
| Publisher | Wiley-Blackwell |
| Publisher Date | 2018-05-22 |
| Access Restriction | Open |
| Subject Keyword | Journal: Angewandte Chemie International Edition Dinitrogen Reduction Nitrogen Fixation Phosphonium Salts |
| Content Type | Text |
| Resource Type | Article |
| Subject | Chemistry Catalysis |
