Reactions of complex ligands

Jahr, Holger C.; Nieger, Martin; Dötz, Karl Heinz

doi:10.1016/s0022-328x(01)01299-2

Cited by 28 publications

(17 citation statements)

References 15 publications

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“…The regioselectivity of the cyclization depends on the solvent used; while in THF the ortho product 93a is slightly favored, a marked 12 : 1 preference for para annulation is observed in toluene, giving 93b as the major isomer. A similar competition of angular versus linear benzannulation has recently been observed in the dibenzofuran series (Scheme 36) [80]. The results obtained for carbene complex 94 suggest that the regiochemistry depends on the substitution pattern of the alkyne and, moreover, that this has an influence on whether or not the chromium fragment remains coordinated to the annulation product.…”

Section: Angular Linear and Other Fused Polycyclic Arenessupporting

confidence: 75%

The Chromium‐Templated Carbene Benzannulation Approach to Densely Functionalized Arenes (Dötz Reaction)

Dötz

Stendel

2002

Modern Arene Chemistry

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The benzannulation of readily accessible aryl-or vinylcarbene chromium complexes by alkynes provides a straightforward synthesis of densely functionalized benzenoid and fused arenes selectively labeled with a Cr(CO) 3 fragment. The reaction occurs under mild conditions, is regioselective, and tolerates a variety of functional groups both on the alkyne and on the carbene ligand. The chromium fragment undergoes a haptotropic metal migration controlled by the substitution pattern of the arene; moreover, it activates the coordinated benzene ring towards selective nucleophilic addition and aromatic substitution. Final decomplexation occurs upon ligand exchange or oxidation reactions. Chiral information imposed on either the carbene ligand or the alkyne allows for a diastereoselective benzannulation providing optically active arene-Cr(CO) 3 complexes. 8.1

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Section: Angular Linear and Other Fused Polycyclic Arenessupporting

confidence: 75%

The Chromium‐Templated Carbene Benzannulation Approach to Densely Functionalized Arenes (Dötz Reaction)

Dötz

Stendel

2002

Modern Arene Chemistry

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“…This reaction has been reported for the substituted naphthalene Cr(CO) 3 complexes [33] and accounts for the presence of regioisomers of different thermodynamic stability [28].…”

Section: Structuresupporting

confidence: 62%

Syntheses of chromium tricarbonyl organometals of 1-methyl-naphthalene and different polycyclic aromatic hydrocarbons, characterisation of the (C11H10)Cr(CO)3 isomers and the crystal structure of the [(η6-5,6,7,8,9,10-C11H10)Cr(CO)3] complex

Arrais

Diana

Marabello

et al. 2011

Journal of Organometallic Chemistry

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“…The obtained results concord with the η 6 –η 6 haptotropic migration of the (CO) 3 Cr fragment from the terminal C 6 ring to the central C 5 N ring which has been attained through a loss of energy; however, its η 6 –η 6 haptotropic migration from central C 5 N ring to the terminal C 6 rings has been achieved by a gain of energy. It is worth to note that (CO) 3 Cr haptotropic rearrangement has been the subject of extensive experimental and theoretical investigations and it has more recently been extended to PAH and heteropolycyclic aromatic hydrocarbons such as phenanthrene,20, 21 benzonaphtofuran,43–46 and complexes with more extended arene platforms 47, 48…”

Section: Resultsmentioning

confidence: 99%

Electronic structure and coordination chemistry of phenanthridine ligand in first‐row transition metal complexes: A DFT study

Benmachiche

Zendaoui

Bouaoud

et al. 2012

Int J of Quantum Chemistry

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The geometric parameters, electronic structures, and haptotropic migration of a series of hypothetical compounds of general formula CpM(C13H9N) and (CO)3M(C13H9N) (M = fist row transition metal, Cp = C5H5, and C13H9N = phenanthridine ligand) are investigated by means of the density functional theory. The phenanthridine ligand can bind to the metal through η1 to η6 coordination mode, in agreement with the electron count and the nature of the metal, showing its capability to adapt itself to the electronic demand of the metal as well as to the polycyclic aromatic hydrocarbons. In the investigated species, the most favored closed‐shell count is 18‐electron except for the Ti and V models which are deficient open‐shell 16‐electron configuration. This study has shown the difference in coordination ability of this heteropolycyclic ligand: the coordination of the central C5N ring is less favored than the terminal C6 rings, in agreement with the π‐electron density localization. Most of the investigated complexes are expected to exhibit a rich fluxional behavior. This flexibility favors the possibility for the existence of several isomers as well as their interconversion through haptotropic shifts. © 2012 Wiley Periodicals, Inc.

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Reactions of complex ligands

Cited by 28 publications

References 15 publications

The Chromium‐Templated Carbene Benzannulation Approach to Densely Functionalized Arenes (Dötz Reaction)

The Chromium‐Templated Carbene Benzannulation Approach to Densely Functionalized Arenes (Dötz Reaction)

Syntheses of chromium tricarbonyl organometals of 1-methyl-naphthalene and different polycyclic aromatic hydrocarbons, characterisation of the (C11H10)Cr(CO)3 isomers and the crystal structure of the [(η6-5,6,7,8,9,10-C11H10)Cr(CO)3] complex

Electronic structure and coordination chemistry of phenanthridine ligand in first‐row transition metal complexes: A DFT study

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