Cluster-stabilized cations: synthesis, structures, molecular dynamics and reactivity

McGlinchey, Michael J.; Girard, Luc; Ruffolo, Ralph

doi:10.1016/0010-8545(95)01131-8

Cited by 87 publications

(55 citation statements)

References 124 publications

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“…Reaction with these cations is highly predictable in regiochemistry. Nucleophiles attack at the propargylic site exclusively; allene formation without prior loss of the Co 2 (CO) 6 unit has never been reported, to our knowledge. Elimination of H + to an enyne complex can compete, but normally can be overridden by the nucleophilic attack process.…”

Section: Introductionmentioning

confidence: 99%

“…Mayr has given an analogous reactivity treatment to the reactions of vinyl substituted alkynedicobalt complexes (6) with electrophiles in order to generate the propargyl cation [21]. Here, there is not a good correlation between the stability of the ultimately formed propargylium cation and the reactivity of the precursor alkene.…”

Section: Fundamental Propertiesmentioning

confidence: 99%

“…Relevant structural features of 2 include distinct differences in each of the sets of the two C α + -Co distances (0.26 and 0.36 Å) for the two Co 2 (CO) 6 units, substantial dihedral angles about the C α -CC-C α' bonds (43 o and 55 o ), and a nearly perfect sp 2 hybridized, trigonal planar orientation at the propargylic carbon. Curiously, DFT optimized geometries neutral ynamine-Co 2 (CO) 6 complexes have a complementary effect, showing a lengthening of one alkynyl C-Co bond and a planar N atom, evidence of contribution of resonance form 3 (Fig. (2)) [15].…”

Section: Fundamental Propertiesmentioning

confidence: 99%

“…EHMO calculations suggest a modest stabilization is possible [23]. (CO) 6 Co 2 (Ph 3 P)(CO) 5 Co 2 (Ph 3 P)(CO) 5 Co 2 (CO) 6 Co 2 Fig. (3).…”

Section: Fundamental Propertiesmentioning

confidence: 99%

“…Some authors active in this field have written accounts of their own work [3,4]. In additions, more comprehensive reviews have appeared which contain sections on propargyl cation cobalt complexes [5,6,7]. The range of nucleophiles capable of attacking these cations is extensive.…”

Section: Introductionmentioning

confidence: 99%

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Chemistry of Propargyldicobalt Cations Recent Developments in the Nicholas and Related Reactions

Green

2001

COC

146

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Abstract:The chemistry of propargyldicobalt cations, also known as the Nicholas reaction, is reviewed, with a focus on the developments since 1995. Advances in the understanding of the fundamental properties, such as structure, stability, and reactivity, of both the hexacarbonyl complexes and those bearing other ligands are discussed. All reactions involving propargyl cation dicobalt complexes are covered, including those stemming from ionization of propargylic leaving groups and those created by electrophilic addition to enyne complexes. Migration reactions involving either initiation or termination by propargyl cation complexes are included, as are the generation and reactions of propargyldicobalt radicals. Cyclization reactions employing these cations have received much attention, in cases with the alkynedicobalt unit located in both exocyclic and endocyclic positions, and these reports are described. Particular attention is paid to preparation of medium ring cycloalkyne complexes and their heterocyclic analogues. In addition, there is discussion of the progress in the in selectivity of these reactions, especially in terms of introduction of asymmetry at the propargylic site. Finally, recent applications of Nicholas reaction chemistry in the synthesis of natural products and related compounds are reported.

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Section: Introductionmentioning

confidence: 99%

Section: Fundamental Propertiesmentioning

confidence: 99%

Section: Fundamental Propertiesmentioning

confidence: 99%

“…EHMO calculations suggest a modest stabilization is possible [23]. (CO) 6 Co 2 (Ph 3 P)(CO) 5 Co 2 (Ph 3 P)(CO) 5 Co 2 (CO) 6 Co 2 Fig. (3).…”

Section: Fundamental Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chemistry of Propargyldicobalt Cations Recent Developments in the Nicholas and Related Reactions

Green

2001

COC

146

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Synthese und Struktur eines [Co2(CO)6]- komplexierten Propargylkations

et al. 1998

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Stereochemical Nonrigidity of Organometallic Complexes

Faller¹

2005

Encyclopedia of Inorganic Chemistry

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Compounds that undergo intramolecular rearrangements at rates that affect the NMR line shapes in generally accessible temperature ranges are described as stereochemically nonrigid. Analysis of 1D and 2D NMR spectra as a function of temperature often allow the rates, as well as the mechanisms of interconversion of conformers or isomers, to be determined. Examples were selected to illustrate the importance of stereochemical nonrigidity in reactivity and the potential for affecting stereochemistry in the products of reactions.

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Cluster-stabilized cations: synthesis, structures, molecular dynamics and reactivity

Cited by 87 publications

References 124 publications

Chemistry of Propargyldicobalt Cations Recent Developments in the Nicholas and Related Reactions

Chemistry of Propargyldicobalt Cations Recent Developments in the Nicholas and Related Reactions

Synthese und Struktur eines [Co2(CO)6]- komplexierten Propargylkations

Stereochemical Nonrigidity of Organometallic Complexes

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