FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2608860073> ?p ?o ?g. }

• W2608860073 endingPage "6012" @default.
• W2608860073 startingPage "5998" @default.
• W2608860073 abstract "The syntheses, interconversions, and spectroscopic properties of a set of iron carbonyl clusters containing an interstitial carbide are reported. This includes the low temperature X-ray structures of the six-iron clusters (Y)2[Fe6(μ6-C)(μ2-CO)4(CO)12] (1a–c; where Y = NMe4, NEt4, PPh4); the five-iron cluster [Fe5(μ5-C)(CO)15] (3); and the novel formulation of the five-iron cluster (NMe4)2[Fe5(μ5-C)(μ2-CO)(CO)13] (4). Also included in this set is the novel charge-neutral cluster, [Fe6(μ6-C)(CO)18] (2), for which we were unable to obtain a crystallographic structure. As synthetic proof for the identity of 2, we performed a closed loop of interconversions within a family of crystallographically defined species (1, 3, and 4): [Fe6]2– → [Fe6]0 → [Fe5]0 → [Fe5]2– → [Fe6]2–. The structural, spectroscopic, and electronic properties of this “missing link” cluster 2 were investigated by IR, Raman, XPS, and Mössbauer spectroscopies—as well as by DFT calculations. A single νCO feature (1965 cm–1) in the IR spectrum of 2, as well as a prominent Raman feature (νsymm = 1550 cm–1), are consistent with the presence of terminal carbonyls and a {(μ6-C)Fe6} arrangement of iron centers around the central carbide. The XPS of 2 exhibits a higher energy Fe 2p3/2 feature (707.4 eV) as compared to that of 1 (705.5 eV), consistent with the two-electron oxidation induced by treatment of 1 with two equivalents of [Fc](PF6) under CO atmosphere (for the two added CO ligands). DFT calculations indicate two axial and four equatorial Fe sites in 1, all of which have the same or similar oxidation states, for example, two Fe(0) and four Fe(+0.5). These assignments are supported by Mössbauer spectra for 1, which exhibit two closely spaced quadrupole doublets with δ = 0.076 and 0.064 mm s–1. The high-field Mössbauer spectrum of 2 (4.2 K) exhibits three prominent quadrupole doublets with δ = −0.18, −0.11, and +0.41 mm s−1. This indicates three pairs of chemically equivalent Fe sites. The first two pairs arise from irons of a similar oxidation state, while the last pair arises from irons in a different oxidation state, indicating a mixed-valent cluster. Variable field Mössbauer spectra for 2 were simulated assuming these two groups and a diamagnetic ground state. Taken together, the Mössbauer results and DFT calculations for 2 indicate two axial Fe(II) sites and four equatorial sites of lower valence, probably Fe(0). In the DFT optimized pentagonal bipyramidal structure for 2, the Fe(II)–Ccarbide distances are compressed (∼1.84 Å), while the Fe(0)–Ccarbide distances are elongated (∼2.05 Å). Analysis of the formulations for 1 (closo-square bipyramid) and 2 (nido-pentagonal bipyramid) is considered in the context of the textbook electron-counting rules of 14n+2 and 14n+4 for closo and nido clusters, respectively. This redox-dependent intracluster disproportionation of Fe oxidation states is concluded to arise from changes in bonding to the central carbide. A similar phenomenon may be promoted by the central carbide of the FeMoco cluster of nitrogenase, which may in turn stimulate N2 reduction." @default.
• W2608860073 created "2017-05-05" @default.
• W2608860073 creator A5017929585 @default.
• W2608860073 creator A5053666065 @default.
• W2608860073 creator A5057043704 @default.
• W2608860073 creator A5069253317 @default.
• W2608860073 creator A5079868859 @default.
• W2608860073 creator A5087988588 @default.
• W2608860073 creator A5088196213 @default.
• W2608860073 creator A5088460503 @default.
• W2608860073 date "2017-04-25" @default.
• W2608860073 modified "2023-10-03" @default.
• W2608860073 title "Structures, Interconversions, and Spectroscopy of Iron Carbonyl Clusters with an Interstitial Carbide: Localized Metal Center Reduction by Overall Cluster Oxidation" @default.
• W2608860073 cites W1503999180 @default.
• W2608860073 cites W1536982351 @default.
• W2608860073 cites W1965148336 @default.
• W2608860073 cites W1966929595 @default.
• W2608860073 cites W1969635440 @default.
• W2608860073 cites W1985713960 @default.
• W2608860073 cites W1986551408 @default.
• W2608860073 cites W1992308919 @default.
• W2608860073 cites W2010193877 @default.
• W2608860073 cites W2011481809 @default.
• W2608860073 cites W2012018675 @default.
• W2608860073 cites W2013072084 @default.
• W2608860073 cites W2015717310 @default.
• W2608860073 cites W2016699440 @default.
• W2608860073 cites W2017804992 @default.
• W2608860073 cites W2018493179 @default.
• W2608860073 cites W2031996907 @default.
• W2608860073 cites W2033164164 @default.
• W2608860073 cites W2033550030 @default.
• W2608860073 cites W2035232298 @default.
• W2608860073 cites W2038091383 @default.
• W2608860073 cites W2038742709 @default.
• W2608860073 cites W2040870163 @default.
• W2608860073 cites W2042745126 @default.
• W2608860073 cites W2063131444 @default.
• W2608860073 cites W2063334178 @default.
• W2608860073 cites W2066239577 @default.
• W2608860073 cites W2072882347 @default.
• W2608860073 cites W2074589905 @default.
• W2608860073 cites W2079363233 @default.
• W2608860073 cites W2081159989 @default.
• W2608860073 cites W2082448227 @default.
• W2608860073 cites W2116357184 @default.
• W2608860073 cites W2131267323 @default.
• W2608860073 cites W2131350133 @default.
• W2608860073 cites W2132601648 @default.
• W2608860073 cites W2133814423 @default.
• W2608860073 cites W2158012127 @default.
• W2608860073 cites W2285287812 @default.
• W2608860073 cites W2314298586 @default.
• W2608860073 cites W2329763230 @default.
• W2608860073 cites W2332259249 @default.
• W2608860073 cites W2332469143 @default.
• W2608860073 cites W2335145042 @default.
• W2608860073 cites W2340647107 @default.
• W2608860073 cites W2350492890 @default.
• W2608860073 cites W28595084 @default.
• W2608860073 cites W2952529537 @default.
• W2608860073 cites W3005413546 @default.
• W2608860073 cites W4239717242 @default.
• W2608860073 doi "https://doi.org/10.1021/acs.inorgchem.7b00741" @default.
• W2608860073 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/6526005" @default.
• W2608860073 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/28605580" @default.
• W2608860073 hasPublicationYear "2017" @default.
• W2608860073 type Work @default.
• W2608860073 sameAs 2608860073 @default.
• W2608860073 citedByCount "22" @default.
• W2608860073 countsByYear W26088600732017 @default.
• W2608860073 countsByYear W26088600732018 @default.
• W2608860073 countsByYear W26088600732019 @default.
• W2608860073 countsByYear W26088600732020 @default.
• W2608860073 countsByYear W26088600732021 @default.
• W2608860073 countsByYear W26088600732022 @default.
• W2608860073 countsByYear W26088600732023 @default.
• W2608860073 crossrefType "journal-article" @default.
• W2608860073 hasAuthorship W2608860073A5017929585 @default.
• W2608860073 hasAuthorship W2608860073A5053666065 @default.
• W2608860073 hasAuthorship W2608860073A5057043704 @default.
• W2608860073 hasAuthorship W2608860073A5069253317 @default.
• W2608860073 hasAuthorship W2608860073A5079868859 @default.
• W2608860073 hasAuthorship W2608860073A5087988588 @default.
• W2608860073 hasAuthorship W2608860073A5088196213 @default.
• W2608860073 hasAuthorship W2608860073A5088460503 @default.
• W2608860073 hasBestOaLocation W26088600732 @default.
• W2608860073 hasConcept C120665830 @default.
• W2608860073 hasConcept C121332964 @default.
• W2608860073 hasConcept C164866538 @default.
• W2608860073 hasConcept C175708663 @default.
• W2608860073 hasConcept C178790620 @default.
• W2608860073 hasConcept C185592680 @default.
• W2608860073 hasConcept C199360897 @default.
• W2608860073 hasConcept C40003534 @default.
• W2608860073 hasConcept C41008148 @default.
• W2608860073 hasConcept C46141821 @default.
• W2608860073 hasConcept C5335593 @default.

• next