The Co+·CO2 electrostatic complex: Geometry and potential

Asher, R.L.; Bellert, D.; Buthelezi, T.; Brucat, P.J.

doi:10.1016/0009-2614(94)00890-6

Cited by 51 publications

(38 citation statements)

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“…In Table we present the bond dissociation energy (BDE) of M +/0/– –OCO energies with respect to the ground-state SR (M +/0/– + CO 2 ) using 20 methods, and compare them to the known experimental data. − For V + –OCO, the computed BDEs using most methods are in good agreement with the experimental data except HF, HFS, BP86, BMK, BH&HLYP, and M11. B3LYP and CCSD(T) are the best.…”

Section: Resultsmentioning

confidence: 71%

Reaction of CO₂ with Atomic Transition Metal M^+/0/– Ions: A Theoretical Study

Sun

Huang

2018

J. Phys. Chem. A

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The activation of carbon dioxide mediated by the first row 3d transition metal (TM) M atomic ions was studied theoretically. Theoretical calculations show left-hand transition-metal ions Sc, Sc, Ti, Ti, and V can mediate oxygen atom transfer (OAT) from carbon dioxide. In the anionic system, for early transition metal ions (Sc to Cr), [OM-CO] are more stable than [M-OCO], while the others favor binding formation, [M-OCO]. TSR was observed in O atom transfer. The OAT reaction is exothermic only for the first three transition metal cations and atoms (Sc, Ti, and V), Fe and all the anions except Cu and Zn. Furthermore, in most case, reaction enthalpy, and energy barrier of OAT for the cationic system is the highest, and the anionic system is the lowest. We discuss the performances of 18 methods on the energies and structures.

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Section: Resultsmentioning

confidence: 71%

Reaction of CO₂ with Atomic Transition Metal M^+/0/– Ions: A Theoretical Study

Sun

Huang

2018

J. Phys. Chem. A

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“…CO 2 binding to Co + is reasonably strong. Experimentally, Asher et al determined a dissociation energy, D 0 (Co + –CO 2 ) > 6960 cm –1 , whereas recent CCSD(T) investigations by Sodupe et al places this value at ca. 7450 cm –1 .…”

Section: Resultsmentioning

confidence: 98%

Infrared Spectroscopy of Gas-Phase M⁺(CO₂)_n (M = Co, Rh, Ir) Ion–Molecule Complexes

et al. 2017

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The structures of gas-phase M(CO) (M = Co, Rh, Ir; n = 2-15) ion-molecule complexes have been investigated using a combination of infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy and density functional theory. The results provide insight into fundamental metal ion-CO interactions, highlighting the trends with increasing ligand number and with different group 9 ions. Spectra have been recorded in the region of the CO asymmetric stretch around 2350 cm using the inert messenger technique and their interpretation has been aided by comparison with simulated infrared spectra of calculated low-energy isomeric structures. All vibrational bands in the smaller complexes are blue-shifted relative to the asymmetric stretch in free CO, consistent with direct binding to the metal center dominated by charge-quadrupole interactions. For all three metal ions, a core [M(CO)] structure is identified to which subsequent ligands are less strongly bound. No evidence is observed in this size regime for complete activation or insertion reactions.

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“…[6] In contrast, cationic metal-CO 2 complexes, [M À (CO 2 ) n ] + , have so far shown to exclusively coordinate CO 2 "end-on" to the metal due to the electron deficiency resulting in electrostatic bonding between the positively charged metal atom and the partial negative charge on oxygen in CO 2 . [7] Here, we present first spectroscopic evidence of an anionic unimetallic Mgcontaining complex with a bidentate double oxygen M(h 2 -O 2 C) coordination, a binding motif that has, so far, only been encountered in bimetallic complexes (structure (C) in Scheme 1).…”

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confidence: 83%

“…In neutral complexes containing a single metal atom monodentate coordination M(h 1 -CO 2 ) or bidentate coordination M(h 2 -CO 2 ) are most common, corresponding to structures (A) and (B) in Scheme 1, respectively. [7] Here, we present first spectroscopic evidence of an anionic unimetallic Mgcontaining complex with a bidentate double oxygen M(h 2 -O 2 C) coordination, a binding motif that has, so far, only been encountered in bimetallic complexes (structure (C) in Scheme 1). [5b] Work on isolated anionic metal-CO 2 complexes is scarce, but [MÀ(CO 2 ) n ] À complexes also prefer the coordination modes A and B, retaining a bent CO 2 moiety as a result of the partial negative charge transfer into the p* orbital of CO 2 .…”

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confidence: 97%

Spectroscopic Identification of a Bidentate Binding Motif in the Anionic Magnesium–CO₂ Complex ([ClMgCO₂]⁻)

et al. 2014

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A magnesium complex incorporating a novel metal-CO2 binding motif is spectroscopically identified. Here we show with the help of infrared photodissociation spectroscopy that the complex exists solely in the [ClMg(η(2) -O2 C)](-) form. This bidentate double oxygen metal-CO2 coordination has previously not been observed in neutral nor in charged unimetallic complexes. The antisymmetric CO2 stretching mode in [ClMg(η(2) -O2 C)](-) is found at 1128 cm(-1) , which is considerably redshifted from the corresponding mode in bare CO2 at 2349 cm(-1) , suggesting that the CO2 moiety has a considerable negative charge (∼1.8 e(-) ). We also employed electronic structure calculations and kinetic analysis to support the interpretation of the experimental results.

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The Co+·CO2 electrostatic complex: Geometry and potential

Cited by 51 publications

References 5 publications

Reaction of CO₂ with Atomic Transition Metal M^+/0/– Ions: A Theoretical Study

Reaction of CO₂ with Atomic Transition Metal M^+/0/– Ions: A Theoretical Study

Infrared Spectroscopy of Gas-Phase M⁺(CO₂)_n (M = Co, Rh, Ir) Ion–Molecule Complexes

Spectroscopic Identification of a Bidentate Binding Motif in the Anionic Magnesium–CO₂ Complex ([ClMgCO₂]⁻)

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The Co+·CO2 electrostatic complex: Geometry and potential

Cited by 51 publications

References 5 publications

Reaction of CO2 with Atomic Transition Metal M+/0/– Ions: A Theoretical Study

Reaction of CO2 with Atomic Transition Metal M+/0/– Ions: A Theoretical Study

Infrared Spectroscopy of Gas-Phase M+(CO2)n (M = Co, Rh, Ir) Ion–Molecule Complexes

Spectroscopic Identification of a Bidentate Binding Motif in the Anionic Magnesium–CO2 Complex ([ClMgCO2]−)

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Reaction of CO₂ with Atomic Transition Metal M^+/0/– Ions: A Theoretical Study

Reaction of CO₂ with Atomic Transition Metal M^+/0/– Ions: A Theoretical Study

Infrared Spectroscopy of Gas-Phase M⁺(CO₂)_n (M = Co, Rh, Ir) Ion–Molecule Complexes

Spectroscopic Identification of a Bidentate Binding Motif in the Anionic Magnesium–CO₂ Complex ([ClMgCO₂]⁻)