Labeled oxygen difluoride—O17,18

Reinhard, R.R.; Arkell, A.

doi:10.1016/0020-708x(65)90010-4

Cited by 9 publications

(9 citation statements)

References 2 publications

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“…These laser-ablated metal atoms were codeposited with 3–4 mmol of argon (Matheson, research grade) containing 1.0 or 2.0% OF 2 (Ozark–Mahoning) onto a CsI cryogenic window for 60 min. The 18 OF 2 sample (91% 18 O enriched) was synthesized and kindly provided by Arkell and co-workers . Both OF 2 and 18 OF 2 samples were used without further purification in a passivated stainless-steel vacuum manifold.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…The 18 OF 2 sample (91% 18 O enriched) was synthesized and kindly provided by Arkell and coworkers. 20 Both OF 2 and 18 OF 2 samples were used without further purification in a passivated stainless-steel vacuum manifold. FTIR spectra were recorded at 0.5 cm −1 resolution on a Nicolet 750 FTIR instrument with a HgCdTe range B detector.…”

Section: ■ Introductionmentioning

confidence: 99%

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Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules

et al. 2019

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A collection of 3d transition metal (V, Mn, Fe, Co, and Ni) oxyfluorides were prepared via the reactions of laser-ablated metal atoms and OF2 in an argon matrix, and the products were identified by infrared spectroscopy together with 18OF2 substitution. OMF2 is the major product from the reactions of metal atoms and OF2. The tetravalent metal center is coordinated to two fluorine atoms and one oxygen atom. Triatomic OMF molecules were observed in the reactions of V, Mn, Fe, and Co with OF2. In addition to OMF and OMF2, OMnF3 and OFeF3 were also formed presumably via the reactions of OMnF and OFeF with F2 resulting from photodecomposition of OF2. The seldom observed OF radical was produced in all of these experiments. Electronic structure calculations at the density functional theory and molecular orbital theory including electron correlation effects (CCSD(T) and CASPT2) levels are used to aid in the assignment of the structures. For OMF (M = Sc–Mn), the structures are bent and those for M = Fe–Cu are linear. The OMF2 molecules are optimized to be C 2v structures. Both OMF and OMF2 have a high spin ground state, with the exception of OCoF2 in which the ground state quartet is the lower energy structure. The M–O stretching frequency is a sensitive measure of the computational method in terms of the bond angle, the coupling of the M–O and M–F stretches, and the amount of spin on the oxygen. A bonding analysis in terms of the CAS orbitals shows that a number of the structures have a multireference character after M = Cr. Oxidation states of the metal are given based on the CASPT2 results. Heats of formation for the OMF and OMF2 are reported.

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Section: Experimental and Computational Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules

et al. 2019

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“…These laser-ablated metal atoms were codeposited with 3–4 mmol of argon (Matheson, research) containing 1.0% OF 2 (Ozark-Mahoning) onto a CsI cryogenic window for 60 min. The 18 OF 2 sample (91% 18 O enriched) was synthesized and kindly provided by Arkell and co-workers . Both OF 2 and 18 OF 2 samples were cooled to 77 K using liquid N 2 and evacuated to remove residual N 2 and O 2 before use.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…These OF 2 sample (91% 18 O enriched) was synthesized and kindly provided by Arkell and co-workers. 21 Both OF 2 and 18 OF 2 samples were cooled to 77 K using liquid N 2 and evacuated to remove residual N 2 and O 2 before use. Fourier transform infrared (FTIR) spectra were recorded at 0.5 cm −1 resolution on a Nicolet 750 FTIR instrument with a HgCdTe range B detector.…”

Section: ■ Introductionmentioning

confidence: 99%

Infrared Spectroscopic and Theoretical Studies on the OMF₂ and OMF (M = Cr, Mo, W) Molecules in Solid Argon

Wei

Gong

et al. 2017

J. Phys. Chem. A

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Group 6 metal oxide fluoride molecules in the form of OMF and OMF (M = Cr, Mo, W) were prepared via the reactions of laser-ablated metal atoms and OF in excess argon. Product identifications were performed by using infrared spectroscopy, OF samples, and electronic structure calculations. Reactions of group 6 metal atoms and OF resulted in the formation of ternary OCrF, OMoF, and OWF molecules with C symmetry in which the tetravalent metal center is coordinated by one oxygen and two fluorine atoms. Both OCrF and OMoF are computed to possess triplet ground states, and a closed shell singlet is the ground state for OWF. Triatomic OCrF, OMoF, and OWF molecules were also observed during sample deposition. All three molecules were computed to have a bent geometry and quartet ground state. A bonding analysis showed that the OMF molecules have highly ionic M-F bonds. OCrF and OMoF have an M-O double bond composed of a σ bond and a π bond. OWF has an M-O triple bond consisting of a σ bond, a π bond, and a highly delocalized O lone pair forming the other π bond. The M-O bonds in the OMF compounds have triple-bond character for all three metals.

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“…The 18 OF 2 sample (91% 18 O enriched) was synthesized and kindly provided by Arkell and Reinhard. 22 Both OF 2 and 18 OF 2 samples were used without further purification in a passivated stainless steel vacuum manifold. Complimentary experiments were performed ablating solid titanium(II) oxide (Strem Chemicals, Inc.) into 1% F 2 /argon samples using our dedicated, passivated stainless steel manifold for fluorine.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

Infrared spectroscopic and theoretical studies of the OTiF2, OZrF2 and OHfF2 molecules with terminal oxo ligands

et al. 2012

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The isolated group 4 metal oxydifluoride molecules OMF(2) (M = Ti, Zr, Hf) with terminal oxo groups are produced specifically on the spontaneous reactions of metal atoms with OF(2) through annealing in solid argon. The product structures and vibrational spectra are characterized using matrix isolation infrared spectroscopy as well as B3LYP density functional and CCSD(T) frequency calculations. OTiF(2) is predicted to have a planar structure while both OZrF(2) and OHfF(2) possess pyramidal structures, all with singlet ground states. Three infrared absorptions are observed for each product molecule, one M-O and two M-F stretching modes, and assignments of these molecules are further supported by the corresponding (18)O shifts. The molecular orbitals of the group 4 OMF(2) molecules show triple bond character for the terminal oxo groups, which are also supported by an NBO analysis. These molecular orbitals include a σ bond (O(2p) + Ti(sd hybrid)), a normal electron pair π bond (O(2p) + Ti(d)), and a dative π bond arising from O lone pair donation to the overlapping Ti d orbital. The M-O bond dissociation energies for OMF(2) are comparable to those in the diatomic oxide molecules. The OTiF intermediate is also observed through two slightly lower frequency bond stretching modes, and its yield is increased in complementary TiO + F(2) experiments. Finally, the formation of group 4 OMF(2) molecules is highly exothermic due to the weak O-F bonds in OF(2) as well as the strong new MO and M-F bonds formed.

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Labeled oxygen difluoride—O17,18

Cited by 9 publications

References 2 publications

Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules

Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules

Infrared Spectroscopic and Theoretical Studies on the OMF₂ and OMF (M = Cr, Mo, W) Molecules in Solid Argon

Infrared spectroscopic and theoretical studies of the OTiF2, OZrF2 and OHfF2 molecules with terminal oxo ligands

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Labeled oxygen difluoride—O17,18

Cited by 9 publications

References 2 publications

Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules

Infrared Spectroscopic and Theoretical Studies of the 3d Transition Metal Oxyfluoride Molecules

Infrared Spectroscopic and Theoretical Studies on the OMF2 and OMF (M = Cr, Mo, W) Molecules in Solid Argon

Infrared spectroscopic and theoretical studies of the OTiF2, OZrF2 and OHfF2 molecules with terminal oxo ligands

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Infrared Spectroscopic and Theoretical Studies on the OMF₂ and OMF (M = Cr, Mo, W) Molecules in Solid Argon