We probe the separation of ligands from iron tetracarbonyl methyl acrylate (Fe(CO)(CHO) or Fe(CO)MA) induced by the interaction with free electrons. The motivation comes from the possible use of this molecule as a nanofabrication precursor and from the corresponding need to understand its elementary reactions fundamental to the electron-induced deposition. We utilize two complementary electron collision setups and support the interpretation of data by quantum chemical calculations. This way, both the dissociative ionization and dissociative electron attachment fragmentation channels are characterized. Considerable differences in the degree of precursor fragmentation in these two channels are observed. Interesting differences also appear when this precursor is compared to structurally similar iron pentacarbonyl. The present findings shed light on the recent electron-induced chemistry of Fe(CO)MA on a surface under ultrahigh vacuum.
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http://dx.doi.org/10.3762/bjnano.15.66 | DOI Listing |
Dalton Trans
November 2024
Department of Chemistry, University of Georgia, Athens, Georgia, 30602, USA.
The structures and energetics of the binuclear methylphosphinidene complexes of cyclopentadienylruthenium carbonyls of the type [MePRu(CO)Cp] ( = 4, 3, 2, 1) have been investigated for comparison with their previously studied iron analogues. For the tetracarbonyls and tricarbonyls [MePM(CO)Cp] ( = 4, 3) substituting ruthenium for iron has relatively little effect on the energetically preferred structures. Thus such structures have two-electron donor bridging MeP groups with no metal-metal bond for the tetracarbonyls and a metal-metal single bond for the tricarbonyls.
View Article and Find Full Text PDFNat Chem
December 2024
TUM School of Natural Sciences, Department of Chemistry, Catalysis Research Center and Wacker Institute of Silicon Chemistry, Technische Universität Müchen, Garching, Germany.
Nitriles (R-C≡N) have been investigated since the late eighteenth century and are ubiquitous encounters in organic and inorganic syntheses. In contrast, heavier nitriles, which contain the heavier analogues of carbon and nitrogen, are sparsely investigated species. Here we report the synthesis and isolation of a phosphino-silylene featuring an N-heterocyclic carbene-phosphinidene and a highly sterically demanding silyl group as substituents.
View Article and Find Full Text PDFBeilstein J Nanotechnol
July 2024
J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 182 23 Prague, Czech Republic.
We probe the separation of ligands from iron tetracarbonyl methyl acrylate (Fe(CO)(CHO) or Fe(CO)MA) induced by the interaction with free electrons. The motivation comes from the possible use of this molecule as a nanofabrication precursor and from the corresponding need to understand its elementary reactions fundamental to the electron-induced deposition. We utilize two complementary electron collision setups and support the interpretation of data by quantum chemical calculations.
View Article and Find Full Text PDFACS Omega
March 2024
Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.
The structures, energetics, and energetically preferred spin states of methylphosphinidene-bridged binuclear cyclopentadienyliron carbonyl complexes MePFe(CO)Cp ( = 4, 3, 2, and 1) related to the experimentally known (μ-RP)Fe(μ-CO)(CO)Cp (R = cyclohexyl, phenyl, mesityl, and 2,4,6-tBuCH) complexes have been investigated by density functional theory. Singlet structures having a pyramidal pseudotetrahedral phosphorus environment with 18-electron iron configurations are energetically preferred in the tricarbonyl and tetracarbonyl systems MePFe(CO)Cp ( = 4 and 3) with the lowest energy structures of the tricarbonyl very closely resembling the experimentally determined structures. For the more unsaturated dicarbonyl and monocarbonyl systems MePFe(CO)Cp ( = 2 and 1), higher spin state triplet and quintet structures are energetically preferred over singlet structures.
View Article and Find Full Text PDFJ Chem Phys
January 2024
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
The heteronuclear group 14 M-iron tetracarbonyl clusters MFe(CO)4- (M = Si, Ge, Sn) anions have been generated in the gas phase by laser ablation of M-Fe alloys and detected by mass and photoelectron spectroscopy. With the support of quantum chemical calculations, the geometric and electronic structures of MFe(CO)4- (M = Si, Ge, Sn) are elucidated, which shows that all the MFe(CO)4- clusters have the M-Fe bonded, iron-centered, and carbonyl-terminal M-Fe(CO)4 structure with the C2v symmetry and a 2B2 ground state. The M-Fe bond can be considered a double bond, which includes one σ electron sharing bond and one π dative bond.
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