Collision-Induced Dissociation Studies of Co(CO)x+, x = 1-5: Sequential Bond Energies and the Heat of Formation of Co(CO)4

Goebel, Susanne; Haynes, Chris L.; Khan, Farooq; Armentrout, P. B.

doi:10.1021/ja00131a023

Cited by 78 publications

(97 citation statements)

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“…[27] In the gas phase, electron-impact studies demonstrated the existence of the series of cations [Co(CO) n ] + (g) (n = 1-5) and the CoÀCO bonding energies were determined. [28] Laser ablation of cobalt in a CO atmosphere and isolation of the products in low-temperature matrices provided evidence for [Co(CO) n ] + (n = 1, 2). [29] A report on the synthesis of [Co(CO) 4 ] 8 ] was recently published.…”

Section: A C H T U N G T R E N N U N G Lution [Co(co) 5 ]A C H T U N mentioning

confidence: 99%

Salts of the Cobalt(I) Complexes [Co(CO)₅]⁺ and [Co(CO)₂(NO)₂]⁺ and the Lewis Acid–Base Adduct [Co₂(CO)₇COB(CF₃)₃]

Bernhardt¹,

Finze²,

Willner³

et al. 2006

Chemistry A European J

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The reaction of [Co(2)(CO)(8)] with (CF(3))(3)BCO in hexane leads to the Lewis acid-base adduct [Co(2)(CO)(7)CO--B(CF(3))(3)] in high yield. When the reaction is performed in anhydrous HF solution [Co(CO)(5)][(CF(3))(3)BF] is isolated. The product contains the first example of a homoleptic metal pentacarbonyl cation with 18 valence electrons and a trigonal-bipyramidal structure. Treatment of [Co(2)(CO)(8)] or [Co(CO)(3)NO] with NO(+) salts of weakly coordinating anions results in mixed crystals containing the [Co(CO)(5)](+)/[Co(CO)(2)(NO)(2)](+) ions or pure novel [Co(CO)(2)(NO)(2)](+) salts, respectively. This is a promising route to other new metal carbonyl nitrosyl cations or even homoleptic metal nitrosyl cations. All compounds were characterized by vibrational spectroscopy and by single-crystal X-ray diffraction.

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Section: A C H T U N G T R E N N U N G Lution [Co(co) 5 ]A C H T U N mentioning

confidence: 99%

Salts of the Cobalt(I) Complexes [Co(CO)₅]⁺ and [Co(CO)₂(NO)₂]⁺ and the Lewis Acid–Base Adduct [Co₂(CO)₇COB(CF₃)₃]

Bernhardt¹,

Finze²,

Willner³

et al. 2006

Chemistry A European J

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“…4 Gas-phase metal carbonyl ions have been studied extensively in mass spectrometry, [5][6][7] and the structures and bonding of these ions have been investigated with theory. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] The reactions of carbonyl ions have been well characterized, and bond energies have been determined, [21][22][23][24][25][26][27][28][29][30][31] but there is much less data on their spectroscopy. However, recent experiments have employed photoelectron spectroscopy to study a variety of metal carbonyl anions, providing vibrational information for the corresponding neutral ground states.…”

Section: Introductionmentioning

confidence: 99%

IR Photodissociation Spectroscopy and Theory of Au⁺(CO)_n Complexes: Nonclassical Carbonyls in the Gas Phase

et al. 2008

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Au+(CO)n complexes are produced in the gas phase via pulsed laser vaporization, expanded in a supersonic jet, and detected with a reflectron time-of-flight mass spectrometer. Complexes up to n = 12 are observed, with mass channels corresponding to the n = 2 and n = 4 showing enhanced intensity. To investigate coordination and structure, individual complexes are mass-selected and probed with infrared photodissociation spectroscopy. Spectra in the carbonyl stretching region are measured for the n = 3−7 species, but no photodissociation is observed for n = 1, 2 due to the strong metal cation-ligand binding. The carbonyl stretch in these systems is blue-shifted 50−100 cm-1 with respect to the free CO vibration (2143 cm-1), providing evidence that these species are so-called "nonclassical" metal carbonyls. Theory at the MP2 and CCSD(T) levels provides structures for these complexes and predicted spectra to compare to the experiment. Excellent agreement is obtained between experiment and theory, establishing that the n = 3 complex is trigonal planar and the n = 4 complex is tetrahedral. Disciplines Chemistry CommentsReprinted (adapted) ReceiVed: NoVember 21, 2007; In Final Form: December 18, 2007 Au + (CO) n complexes are produced in the gas phase via pulsed laser vaporization, expanded in a supersonic jet, and detected with a reflectron time-of-flight mass spectrometer. Complexes up to n ) 12 are observed, with mass channels corresponding to the n ) 2 and n ) 4 showing enhanced intensity. To investigate coordination and structure, individual complexes are mass-selected and probed with infrared photodissociation spectroscopy. Spectra in the carbonyl stretching region are measured for the n ) 3-7 species, but no photodissociation is observed for n ) 1, 2 due to the strong metal cation-ligand binding. The carbonyl stretch in these systems is blue-shifted 50-100 cm -1 with respect to the free CO vibration (2143 cm -1 ), providing evidence that these species are so-called "nonclassical" metal carbonyls. Theory at the MP2 and CCSD(T) levels provides structures for these complexes and predicted spectra to compare to the experiment. Excellent agreement is obtained between experiment and theory, establishing that the n ) 3 complex is trigonal planar and the n ) 4 complex is tetrahedral.

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“…There is a growing body of experimental information regarding the interactions of small neutral 1 and cationic [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] clusters of transition metals with compounds containing prototypical bonds ͑e.g., C-H, C-C, N-H, O-H, Si-H, Si-C͒ of importance in catalytic processes. Transition metal-main group complexes have been the focus of intense computational effort.…”

Section: Introductionmentioning

confidence: 99%

An ab initio study of the reaction mechanism of Co++NH3

Taketsugu

Gordon

1997

The Journal of Chemical Physics

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To investigate the mechanism for N-H bond activation by a transition metal, the reactions of Co+(3F,5F) with NH3 have been studied with complete active space self-consistent field (CASSCF), multireference configuration interaction (MR-SDCI), and multireference many body perturbation theory (MRMP) wave functions, using both effective core potential and all-electron methods. Upon their initial approach, the reactants yield an ion-molecule complex, CoNH+3(3E,5A2,5A1), with retention of C3ν symmetry. The Co+=NH3 binding energies are estimated to be 49 (triplet) and 45 (quintet) kcal/mol. Subsequently, the N-H bond is activated, leading to an intermediate complex H-Co-NH+2 (C2ν symmetry), through a threecenter transition state with an energy barrier of 56-60 (triplet) and 70-73 (quintet) kcal/mol. The energy of H-Co-NH+2, relative to that of CoNH+3, is estimated to be 60 to 61 (triplet) and 44 (quintet) kcal/mol. However, the highest levels of theory employed here (including dynamic correlation corrections) suggest that the triplet intermediate HCoNH+2 may not exist as a minimum on the potential energy surface. Following Co-N or H-Co bond cleavage, the complexH-Co-NH+2 leads to HCo++NH2 or H+CoNH+2. Both channels (triplet and quintet) are found to be endothermic by 54-64 kcal/mol. Theoretical study of the water activation by a cobalt cation: Ab initio multireference theory versus density functional theory

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Collision-Induced Dissociation Studies of Co(CO)x+, x = 1-5: Sequential Bond Energies and the Heat of Formation of Co(CO)4

Cited by 78 publications

References 3 publications

Salts of the Cobalt(I) Complexes [Co(CO)₅]⁺ and [Co(CO)₂(NO)₂]⁺ and the Lewis Acid–Base Adduct [Co₂(CO)₇COB(CF₃)₃]

Salts of the Cobalt(I) Complexes [Co(CO)₅]⁺ and [Co(CO)₂(NO)₂]⁺ and the Lewis Acid–Base Adduct [Co₂(CO)₇COB(CF₃)₃]

IR Photodissociation Spectroscopy and Theory of Au⁺(CO)_n Complexes: Nonclassical Carbonyls in the Gas Phase

An ab initio study of the reaction mechanism of Co++NH3

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Collision-Induced Dissociation Studies of Co(CO)x+, x = 1-5: Sequential Bond Energies and the Heat of Formation of Co(CO)4

Cited by 78 publications

References 3 publications

Salts of the Cobalt(I) Complexes [Co(CO)5]+ and [Co(CO)2(NO)2]+ and the Lewis Acid–Base Adduct [Co2(CO)7COB(CF3)3]

Salts of the Cobalt(I) Complexes [Co(CO)5]+ and [Co(CO)2(NO)2]+ and the Lewis Acid–Base Adduct [Co2(CO)7COB(CF3)3]

IR Photodissociation Spectroscopy and Theory of Au+(CO)n Complexes: Nonclassical Carbonyls in the Gas Phase

An ab initio study of the reaction mechanism of Co++NH3

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Salts of the Cobalt(I) Complexes [Co(CO)₅]⁺ and [Co(CO)₂(NO)₂]⁺ and the Lewis Acid–Base Adduct [Co₂(CO)₇COB(CF₃)₃]

Salts of the Cobalt(I) Complexes [Co(CO)₅]⁺ and [Co(CO)₂(NO)₂]⁺ and the Lewis Acid–Base Adduct [Co₂(CO)₇COB(CF₃)₃]

IR Photodissociation Spectroscopy and Theory of Au⁺(CO)_n Complexes: Nonclassical Carbonyls in the Gas Phase