Gas-phase ligand substitution reactions with (OC)Fe(NO)2.bul.-, (OC)2Co(NO).bul.-, (.eta.3-C3H5)Co(CO)2.bul.-, (C3H5)Co(CO)3.bul.-, and CpCo(CO)2.bul.-

McDonald, Richard N.; Schell, Philip L.

doi:10.1021/om00098a019

Cited by 16 publications

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“…We propose that EA[CpCo(CO) 2 ] ) 0.86 ( 0.2 eV. From bracketing experiments, McDonald and Schell 18 have established that EA[(η 3 -C 3 H 5 )Co(CO) 3 ] s EA[CpCo(CO) 2 ] and that EA[(η 3 -C 3 H 5 )Co(CO) 2 ] ) 0.9 ( 0.2 eV, although for the latter complex, the upper bound is not definite. Other work in our group 29 has established that EA[Co(CO) 2 (NO)] ) 1.73 ( 0.03 eV.…”

Section: Discussionmentioning

confidence: 85%

“…They also observed that CpCo(CO) 2 - will react with PF 3 to produce CpCo(CO)(PF 3 ) - with, however, a very low yield. In a flowing afterglow apparatus, McDonald and Schell observed that the main product from the slow reaction of CpCo(CO) 2 - with PF 3 was the total adduct CpCo(PF 3 )(CO) 2 - , with CpCo(CO)(PF 3 ) - being the minor product. The observation of the total adduct is consistent with an associative mechanism for ligand substitution in CpCo(CO) 2 - .…”

Section: Introductionmentioning

confidence: 99%

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An Investigation of the Electronic Structures of CpCo(CO)₂ and CpCo(CO)₂^- Using Experimental and Theoretical Techniques

et al. 1997

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An upper bound for the adiabatic electron affinity of cyclopentadienylcobaltdicarbonyl [CpCo(CO)2] is 0.86 ± 0.2 eV as determined by fixed-frequency negative-ion photoelectron spectroscopy. During the course of the experimental work, the generation of the binuclear complex [CpCo(CO)2]2 - is detected, and, to our knowledge, this is the first observation of this anionic cluster. Electronic structural calculations using both the density functional theory formalism and ab initio techniques are completed for both CpCo(CO)2 and the corresponding negative-ion. A DFT/DZVP2 calculation yields the vertical electron affinity of CpCo(CO)2 as 0.84 ± 1.0 eV. The theoretical results confirm that a weak “allyl-ene” type structure exists in the cyclopentadienyl ligand of both molecules, but the distortion is less pronounced in CpCo(CO)2 - than in CpCo(CO)2. Our results lend further support to the classification of CpCo(CO)2 - as a 19-electron complex.

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Section: Discussionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

An Investigation of the Electronic Structures of CpCo(CO)₂ and CpCo(CO)₂^- Using Experimental and Theoretical Techniques

et al. 1997

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“…Two other detailed 17-electron ligand substitution studies deal with a number of other transition-metal anions: Fe(CO)(NO) 2 - , Co(CO) 2 (NO) - , (η 3 -C 3 H 5 )Co(CO) 2 - , (C 3 H 5 )Co(CO) 3 - , CpCo(CO) 2 - , Fe(CO) 4 - , Cr(CO) 5 - , and Mn(CO) 4 H - . , Their reactions with phosphines, NO, SO 2 , olefins, ketones, O 2 , CO, CO 2 , and COS were studied. The chemistry is complex and difficult to summarize succinctly.…”

Section: Organometallics: Transition-metal Ion−molecule Chemistrymentioning

confidence: 99%

“…None of the 17-electron transition-metal anions studied react with trimethylphosphine. Reactions of these 17-electron anions with dioxygen also are complex, proton-transfer reactions leading to a variety of oxide anions and ligand displacements. ,, For example, Fe(CO)(NO) 2 - undergoes CO substitution, CO and NO displacement, and loss of CO 2 , all believed to arise from the η 1 -superoxide intermediate Fe(CO)(NO) 2 (O−O) - . The complexity of the many anions and reactions studied, although leading to interesting reaction chemistry, yields only limited thermochemical data.…”

Section: Organometallics: Transition-metal Ion−molecule Chemistrymentioning

confidence: 99%

Organometallic Chemistry in the Flowing Afterglow: A Review

Damrauer

2004

Organometallics

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The flowing afterglow technique, among the various mass spectroscopic methods that have been used to study ions and ion−molecule reactions in the gas phase, has provided a number of interesting results in organometallic chemistry. The flowing afterglow technique is particularly suited for the investigation of thermally relaxed species, since ions and ion−molecule reactions are carried out in a pressure regime where multiple collisions with inert gases occur. Many of these studies are reviewed in this paper, with particular emphasis on anionic organometallic chemistry.

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“…This elemental composition may represent a single neutral species or, for example, a CO and a C4H4 molecule. However, loss of CO from the collision complex in the reaction with SO2 is not observed and, in addition, no reaction occurs with NO even though this neutral species is known to be able to displace a CO ligand in organometallic negative ions [10, 30,31]. The loss of CsH40 leads, therefore, to the suggestion that C5H5MnO-ions with a cyclopentadienone and a hydride ligand are formed; that is, ion 8 is generated in the reaction of O'-with CpMn(C0)3 [32].…”

Section: Structures and Formation Of The C5hsmno-and C6h7a4no-ionsmentioning

confidence: 99%

Regioselectivity in the gas-phase reactions of the O− radical anion with (η5-cyclopentadienyl)tricarbonylmanganese(I) and (η5-methylcyclopentadienyl)tricarbonylmanganese(I): formation and structure of C5H5MnO−n and C6H7MnO−n (n = 1, 2) ions

Berg

Ingemann

Nibbering

1994

International Journal of Mass Spectrometry and Ion Processes

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Regioselectivity in the gas-phase reactions of the O-* radical; anion with (n5-cyclopentadienyl) tricarbonylmanganese(I) and (n5-methylcyclopentadienyl) tricarbonylmanganese(I). Formation and structure of C5H5MnO(n)-and C6H7MnO(n)-(n=1,2)ions. van den Berg, K.J.; Ingemann Jorgensen, S.; Nibbering, N.M.M. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. CH$pMn(CO)3, have been studied with Fourier transform ion cyclotron resonance. The main reactions are (i) proton abstraction, (ii) loss of COz, and (iii) expulsion of two or three CO molecules from the collision complex. Initial attack on a CO ligand is the main process as indicated by experiments with '*O'-and the ion/molecule reactions of the product ions resulting from the loss of three CO molecules with water, aliphatic alcohols, methanethiol and SO,. The attack on a CO ligand followed by loss of three CO molecules is suggested to yield C5H5MnO-ions with a (cyclopentadienone)MnHstructure in the reaction with CpMn(C0)3 and (methylcyclopentadienone)MnHions if CH$pMn(C0)3 is the substrate. A possible mechanism for the process leading to the indicated transformation of the Cp and CH,Cp ligands into C5H40 and CH&H30 ligands, respectively, is discussed together with the formation of (fulvene)Mn(OH)-ions following attack of O'-on CH$pMn(CO),. The (cyclopentadienone)MnHand (methylcyclopentadienone)MnHions react with NzO by oxygen atom abstraction to form C5H5MnO; and C6H7MnO; ions, respectively.

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Gas-phase ligand substitution reactions with (OC)Fe(NO)2.bul.-, (OC)2Co(NO).bul.-, (.eta.3-C3H5)Co(CO)2.bul.-, (C3H5)Co(CO)3.bul.-, and CpCo(CO)2.bul.-

Cited by 16 publications

References 0 publications

An Investigation of the Electronic Structures of CpCo(CO)₂ and CpCo(CO)₂^- Using Experimental and Theoretical Techniques

An Investigation of the Electronic Structures of CpCo(CO)₂ and CpCo(CO)₂^- Using Experimental and Theoretical Techniques

Organometallic Chemistry in the Flowing Afterglow: A Review

Regioselectivity in the gas-phase reactions of the O− radical anion with (η5-cyclopentadienyl)tricarbonylmanganese(I) and (η5-methylcyclopentadienyl)tricarbonylmanganese(I): formation and structure of C5H5MnO−n and C6H7MnO−n (n = 1, 2) ions

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Gas-phase ligand substitution reactions with (OC)Fe(NO)2.bul.-, (OC)2Co(NO).bul.-, (.eta.3-C3H5)Co(CO)2.bul.-, (C3H5)Co(CO)3.bul.-, and CpCo(CO)2.bul.-

Cited by 16 publications

References 0 publications

An Investigation of the Electronic Structures of CpCo(CO)2 and CpCo(CO)2- Using Experimental and Theoretical Techniques

An Investigation of the Electronic Structures of CpCo(CO)2 and CpCo(CO)2- Using Experimental and Theoretical Techniques

Organometallic Chemistry in the Flowing Afterglow: A Review

Regioselectivity in the gas-phase reactions of the O− radical anion with (η5-cyclopentadienyl)tricarbonylmanganese(I) and (η5-methylcyclopentadienyl)tricarbonylmanganese(I): formation and structure of C5H5MnO−n and C6H7MnO−n (n = 1, 2) ions

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An Investigation of the Electronic Structures of CpCo(CO)₂ and CpCo(CO)₂^- Using Experimental and Theoretical Techniques

An Investigation of the Electronic Structures of CpCo(CO)₂ and CpCo(CO)₂^- Using Experimental and Theoretical Techniques