Journal Article

PUBDB-2023-00429

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Substrate-Gated Transformation of a Pre-Catalyst into an Iron-Hydride Intermediate [(NO)$_2$ (CO)Fe(μ-H)Fe(CO)(NO)$_2$]$^−$ for Catalytic Dehydrogenation of Dimethylamine Borane

Tseng, Y.-T. (First author) ; Pelmenschikov, V. (Corresponding author) ; Iffland-Mühlhaus, L. ; Calabrese, D. ; Chang, Y.-C. ; Laun, K.Extern* ; Pao, C.-W. ; Sergeev, I.XFEL.EU*DESY* ; Yoda, Y. ; Liaw, W.-F. ; Chen, C.-H. (Corresponding author) ; Hsu, I.-J. (Corresponding author) ; Apfel, U.-P. (Corresponding author) ; Caserta, G. (Corresponding author) ; Lauterbach, L. (Corresponding author) ; Lu, T.-T. (Corresponding author)

2023
American Chemical Society Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.inorgchem.2c03278  doi:10.3204/PUBDB-2023-00429

Abstract: Continued efforts are made on the development of earth-abundant metal catalysts for dehydrogenation/hydrolysis of amine boranes. In this study, complex [K-18-crown-6-ether][(NO)$_2$Fe(μ-$^{Me}$Pyr)(μ-CO)Fe(NO)$_2$] (3-K-crown, $^{Me}$Pyr = 3-methylpyrazolate) was explored as a pre-catalyst for the dehydrogenation of dimethylamine borane (DMAB). Upon evolution of H$_{2(g)}$ from DMAB triggered by 3-K-crown, parallel conversion of 3-K-crown into [(NO)$_2$Fe(N,N′-$^{Me}$PyrBH$_2$NMe$_2$)]− (5) and an iron-hydride intermediate [(NO)$_2$(CO)Fe(μ-H)Fe(CO)(NO)$_2$]$^−$ (A) was evidenced by X-ray diffraction/nuclear magnetic resonance/infrared/nuclear resonance vibrational spectroscopy experiments and supported by density functional theory calculations. Subsequent transformation of A into complex [(NO)$_2$Fe(μ-CO)$_2$Fe(NO)$_2$]$^−$ (6) is synchronized with the deactivated generation of H$_{2(g)}$. Through reaction of complex [Na-18-crown-6-ether][(NO)$_2$Fe(η$^2$-BH$_4$)] ($_4$-Na-crown) with CO(g) as an alternative synthetic route, isolated intermediate [Na-18-crown-6-ether][(NO)$_2$(CO)Fe(μ-H)Fe(CO)(NO)$_2$] (A-Na-crown) featuring catalytic reactivity toward dehydrogenation of DMAB supports a substrate-gated transformation of a pre-catalyst [(NO)$_2$Fe(μ-$^{Me}$Pyr)(μ-CO)Fe(NO)$_2$]$^−$ (3) into the iron-hydride species A as an intermediate during the generation of H$_{2(g)}$.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. Experimentebetreuung PETRA III (FS-PET-S)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
3. FS-Proposal: I-20210059 (I-20210059) (I-20210059)
4. FS-Proposal: I-20211258 (I-20211258) (I-20211258)
5. DFG project 390540038 - EXC 2008: Unifying Systems in Catalysis "UniSysCat" (390540038) (390540038)
6. DFG project 390677874 - EXC 2033: RESOLV (Ruhr Explores Solvation) (390677874) (390677874)
7. DFG project 390919832 - EXC 2186: Das Fuel Science Center – Adaptive Umwandlungssysteme für erneuerbare Energie- und Kohlenstoffquellen (390919832) (390919832)

Experiment(s):

1. PETRA Beamline P01 (PETRA III)

Appears in the scientific report 2023

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF < 5 ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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