Chromium-Templated Benzannulation and Haptotropic Metal Migration

Dötz, Karl Heinz; Wenzel, Benjamin; Jahr, Holger C.

doi:10.1007/b99910

Cited by 46 publications

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“…Inter-ring haptotropic rearrangement in which a metal migrates along a polyaromatic system has culminated in the design of organometallic switches. For instance, a recent study by Dötz and co-workers reported that the η 6 −η 6 solution-state inter-ring haptotropic rearrangement of the Cr(CO) 3 arenophile on substituted naphthyl ligands proceeds photochemically in one direction and thermally in the other . Other examples of irreversible and chemically reversible switches using solution-state haptotropic rearrangement of Cr(CO) 3 have also been reported.…”

Section: Introductionmentioning

confidence: 99%

Stereoelectronic Effects of the Arenophile (η⁵-Cp*)Ru⁺in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components

et al. 2006

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The organoiron vinylidene derivatives [(η2-dppe)(η5-Cp*)FeCCH−(1-naphthyl)][X] (Cp* = C5Me5; dppe = 1,2-bis(diphenylphosphino)ethane; X = BPh4, 3[BPh 4 ]; X = PF6, 3[PF 6 ]) were synthesized from (η2-dppe)(η5-Cp*)FeCl and 1-naphthyl acetylene in the presence of NaBPh4 or NaPF6, respectively. The daughter organometallic acetylide complex, (η2-dppe)(η5-Cp*)Fe−C⋮C−(1-naphthyl), 4, was obtained, in 81% yield, upon deprotonation of the vinylidene precursor, 3[BPh 4 ], by t-BuOK in a MeOH/THF mixture at room temperature. One new dicationic heterobimetallic vinylidene Fe(II)−Ru(II) complex, 5[PF 6 ] 2 , was obtained, in 74% yield, upon reaction of the 1-naphthyl vinylidene precursor 3[PF 6 ], with [(η5-Cp*)Ru(CH3CN)3][PF6]. Binuclear acetylides were prepared via η6 complexation of the (η5-Cp*)Ru+ arenophile onto either the substituted or the free naphthyl ring of 1-naphthyl acetylide derivative 4, and both of these haptotropomers, 6A[PF 6 ] and 6B[PF 6 ], were isolated. A third bimetallic model compound, 2[PF 6 ], was prepared in 69% yield via (η5-Cp*Ru) coordination of the ethynyl phenyl ring of the known complex (η2-dppe)(η5-Cp*)Fe−C⋮C−Ph (1). All three complexations are regioselective, occurring only on the acetylenic aryl moiety instead of the competing dppe phenyls. The thermally stable FeIII counterparts, 2[PF 6 ] 2 , 4[PF 6 ], and 6B[PF 6 ] 2 , were obtained (70−86% isolated yield) upon oxidation, in THF at −60 °C, with ferrocenium hexafluorophosphate. All the new compounds were thoroughly authenticated using analytical and spectroscopic methods. In the heterobimetallic species, the aromaticity of the acetylide aryl linker is changed in situ via (i) the complexation of the (η5-Cp*)Ru+ arenophile and (ii) for the case of the 1-naphthyl substituent, by the η6−η6 inter-ring haptotropic migration of this group between naphthyl rings. The upshot is that these compounds exhibit significantly different degrees of electronic communication between the two organometallic termini across the length of the ethynediyl−aryl segment as a function of arenophile location: either (i) collinear to the Fe−C⋮C wire-like segment (2[PF 6 ] and 6A[PF 6 ]) or (ii) on the free ring of the 1-naphthyl moiety (6B[PF 6 ]). To establish the degree of electron transfer within the novel compounds reported herein, their physical properties are compared using NMR, UV-vis, IR, Mössbauer, and electron spin resonance (ESR) spectroscopies, as well as cyclic voltammetry and X-ray crystallography. Accordingly, the solid-state structures of all seven novel, electron-rich organometallic acetylides are described, including both haptotropomers 6A[PF 6 ] and 6B[PF 6 ]. Finally, the first redox-driven inter-ring haptotropic rearrangement of (η5-Cp*)Ru+ between naphthyl rings was shown to occur.

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Section: Introductionmentioning

confidence: 99%

Stereoelectronic Effects of the Arenophile (η⁵-Cp*)Ru⁺in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components

et al. 2006

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“…21 Haptotropic shifts play significant role in transition metal catalysed processes and in designing organometallic switches. 22,23 Exhaustive studies have been done on haptotropic shifts in complexes with aromatic polycyclic ligands, like naphthalene, anthracene where the metal ion moves across the rings. 20,[24][25][26] The simplest system in which haptotropic rearrangement takes place was η 6 -naphthalene-Cr(CO) 3 and its derivatives, which was first reported by Deubzer.…”

Section: Introductionmentioning

confidence: 99%

“…[41][42][43] Generally, the haptotropic migration can be influenced by the incorporation of redox-, photo-or pH-sensitive functional groups in combination with a complementary substitution pattern in the metal moiety and the arene ligand and hence may facilitate the construction of a switchable device. 23 And also, arene-chromium tricarbonyl compounds have attracted considerable attention for many years because of their potential applications in organic synthesis and in designing molecular switches/brakes, etc. 41,43,44 In our previous theoretical work we have reported the structural and electronic effects of cation binding to π system of η 6 -benzene-Cr(CO) 3 .…”

Section: Introductionmentioning

confidence: 99%

Does alkali cation binding to aromatic ring retard the fluxional haptotropic migration? Evidences from density functional study

Kalpana¹,

Akilandeswari²

2017

J Chem Sci

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DFT calculations were performed on the sandwich complexes of naphthalene (MNC) with alkali metal cation (Li + /Na + /K +) on one π face and the tripodal Cr(CO) 3 moiety on the other with a view to explore the role of cation on haptotropic migration. Cation binding not only enhances the complex interaction energy but also delicately affects the fluxionality in the molecule by increasing the barrier to haptotropic shift of Cr(CO) 3. The competing nature of the bifacial acids with sandwiched aromatic ring is established. In line with Pearson's HSAB principle, LiNC system with highest interaction energy is found to be the most stable one among all the systems under study.

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“…The variation of the metal coordination site in π‐coordinated polycyclic aromatic hydrocarbons (PAH) corresponds to the haptotropic rearrangement or haptotropic migration,1–6 in which the metal fragment ML n is considered as the moveable moiety that is shifted between two rings of polycyclic or heteropolycyclic ligands. These structural characteristics and dynamical properties give to this category of transition metal complexes a considerable interest.…”

Section: Introductionmentioning

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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Chromium-Templated Benzannulation and Haptotropic Metal Migration

Cited by 46 publications

References 0 publications

Stereoelectronic Effects of the Arenophile (η⁵-Cp*)Ru⁺in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components

Stereoelectronic Effects of the Arenophile (η⁵-Cp*)Ru⁺in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components

Does alkali cation binding to aromatic ring retard the fluxional haptotropic migration? Evidences from density functional study

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

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Chromium-Templated Benzannulation and Haptotropic Metal Migration

Cited by 46 publications

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Stereoelectronic Effects of the Arenophile (η5-Cp*)Ru+in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components

Stereoelectronic Effects of the Arenophile (η5-Cp*)Ru+in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components

Does alkali cation binding to aromatic ring retard the fluxional haptotropic migration? Evidences from density functional study

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

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Stereoelectronic Effects of the Arenophile (η⁵-Cp*)Ru⁺in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components

Stereoelectronic Effects of the Arenophile (η⁵-Cp*)Ru⁺in Electron-Rich σ-Arylacetylide Iron Complexes Including Redox-Driven Haptotropic Rearrangement: An Approach toward Readable Binary Molecular Memory Components