% IMPORTANT: The following is UTF-8 encoded. This means that in the presence % of non-ASCII characters, it will not work with BibTeX 0.99 or older. % Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or % “biber”. @ARTICLE{Tseng:517394, author = {Tseng, Yu-Ting and Pelmenschikov, Vladimir and Iffland-Mühlhaus, Linda and Calabrese, Donato and Chang, Yu-Che and Laun, Konstantin and Pao, Chih-Wen and Sergeev, Ilya and Yoda, Yoshitaka and Liaw, Wen-Feng and Chen, Chien-Hong and Hsu, I-Jui and Apfel, Ulf-Peter and Caserta, Giorgio and Lauterbach, Lars and Lu, Tsai-Te}, title = {{S}ubstrate-{G}ated {T}ransformation of a {P}re-{C}atalyst into an {I}ron-{H}ydride {I}ntermediate [({NO})$_2$ ({CO}){F}e(μ-{H}){F}e({CO})({NO})$_2$]$^−$ for {C}atalytic {D}ehydrogenation of {D}imethylamine {B}orane}, journal = {Inorganic chemistry}, volume = {62}, number = {2}, issn = {0020-1669}, address = {Washington, DC}, publisher = {American Chemical Society}, reportid = {PUBDB-2023-00429}, pages = {769 - 781}, year = {2023}, 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$_{2(g)}$.}, cin = {DOOR ; HAS-User / FS-PET-S}, ddc = {540}, cid = {I:(DE-H253)HAS-User-20120731 / I:(DE-H253)FS-PET-S-20190712}, pnm = {632 - Materials – Quantum, Complex and Functional Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3) / FS-Proposal: I-20210059 (I-20210059) / FS-Proposal: I-20211258 (I-20211258) / DFG project 390540038 - EXC 2008: Unifying Systems in Catalysis "UniSysCat" (390540038) / DFG project 390677874 - EXC 2033: RESOLV (Ruhr Explores Solvation) (390677874) / DFG project 390919832 - EXC 2186: Das Fuel Science Center – Adaptive Umwandlungssysteme für erneuerbare Energie- und Kohlenstoffquellen (390919832)}, pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3 / G:(DE-H253)I-20210059 / G:(DE-H253)I-20211258 / G:(GEPRIS)390540038 / G:(GEPRIS)390677874 / G:(GEPRIS)390919832}, experiment = {EXP:(DE-H253)P-P01-20150101}, typ = {PUB:(DE-HGF)16}, pubmed = {36580657}, UT = {WOS:000907025800001}, doi = {10.1021/acs.inorgchem.2c03278}, url = {https://bib-pubdb1.desy.de/record/517394}, }