Regioselective synthesis of π-complexes of substituted polycyclic aromatic compounds. Experimental (NMR) and theoretical (DFT) studies of η6,η6-haptotropic rearrangements in naphthalenechromiumtricarbonyl complexes

Oprunenko, Yuri F.; Akhmedov, Novruz G.; Laikov, Dimitri N.; Malyugina, S. G.; Mstislavsky, V. I.; Roznyatovsky, Vitaly A.; Ustynyuk, Yuri A.; Ustynyuk, Nikolai A.

doi:10.1016/s0022-328x(99)00123-0

Cited by 52 publications

(51 citation statements)

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“…As expected from the previous observations of the complexation of other heptalenes, only the on-state complex 23 with (6,7,8,9,10,10a-h)-coordination of the Cr(CO) 3 group and the off-state complexes 22 and 24 with (1,2,3,4,5,5a-h)-and (1,2,3,4,5,5a-h:6,7,8,9,10, [19].…”

supporting

confidence: 87%

“…In summary, we can conclude that the (6,7,8,9,10,10a-h)-coordination of the Cr(CO) 3 group at the heptalene skeleton has no noticeable influence on the UV/VIS behavior of the complexes 11 and 12. On the other hand, the Cr(CO) 3 [22].…”

Section: Methodsmentioning

confidence: 74%

“…These observations are in agreement with the fact that two thermally inducible rearrangements, namely the intra-ring 1,2-shift and inter-ring migration of the Cr(CO) 3 group, could take place during the ÷fele reaction after primary formation of the off-state complexes via directing assistance of the ester groups. Furthermore, we assume that complexes 17 and 19 with (1,2,3,4,5,10a-h)-coordination are kinetically controlled products and will undergo thermal rearrangements to the thermodynamically more stable isomers with (6,7,8,9,10,10a-h)-coordination. To verify this assumption, the thermal isomerizations of complexes 16 ± 20 have been investigated (Schemes 8 and 9).…”

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confidence: 99%

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Synthesis and Properties of Novel (Tricarbonyl)(heptalene)chromium Complexes

Ochertyanova

Hansen

Ustynyuk

2002

HCA

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A number of novel (tricarbonyl)chromium complexes of heptalenes 10 ± 13, 16 ± 20 and 23 ± 25 have been prepared by reaction of the heptalenes with [Cr(CO) 3 L 3 ] (LNH 3 , Py; cf. Schemes 3 ± 6). Surprisingly, the offstate complexes 17 and 19, in which the Cr(CO) 3 group complexes on the diester ring, have been obtained with excellent regioselectivity. The directing effect of ester CO groups on the regioselectivity of the Cr(CO) 3 coordination to heptalene rings has been discussed. These complexes undergo thermal rearrangements via 1,2-intra-ring shift and inter-ring migration of the Cr(CO) 3 fragment to give the thermodynamically more stable on-state complexes 16 and 27, respectively (cf. Schemes 8 and 9). The analogous thermal behavior of other prepared complexes has also been investigated. A new procedure for the selective preparation of complexes 10 and 13, in which the Cr(CO) 3 group is coordinated to the phenyl ring of the styryl substituent has also been developed (Scheme 7). The attachment of the Cr(CO) 3 fragment to the phenyl group has a visible influence on the UV/VIS behavior of the on-state complexes 10 and 13a, as well as on the photochemical behavior of the DBS isomers 13a/13b (cf. Scheme 10). Introduction. ± So far, quite little is known about metallocarbonyl complexes of heptalenes [1], mainly because of the difficulties associated with the synthesis of various substituted heptalenes and their relative instability (cf. [2] [3]). Nevertheless, a number of tricarbonylchromium complexes of heptalenes have been synthesized, and their dynamic behavior has been investigated (Scheme 1) [4].The following events have been established: 1) Two thermally inducible rearrangements proceed in mononuclear complexes 2a ± 2d and 5a ± 5d (Scheme 2): a) intra-ring 1,2-shift (IRS) of the Cr(CO) 3 group and b) inter-ring migration (IRM) of the Cr(CO) 3 group. Both migrations are accompanied by a cyclic CC-bond shift (DBS) at the heptalene skeleton. Direct transformations 2b to 2d, as well as 2a to 2c, without DBS has been excluded [4b]. The thermal inter-ring migration of the Cr(CO) 3 group within complex 5c to yield 5b has been the first example of an inter-ring haptotropic rearrangement in nonplanar complexes of bicyclic p-systems [4a].2) 1,2-Haptotropic shifts and the inter-ring haptotropic migrations of the Cr(CO) 3 group are intramolecular processes. Activation barriers for both processes are quite similar [4].3) The occupancy of all four peri-positions in complexes 5a ± 5d by Me groups leads to activation barriers close to those for purely thermal decomplexation reactions [4a].4) The thermodynamically most stable complex 2a carries the coordinating Cr(CO) 3 group at the seven-membered ring, which is substituted with three electrondonating Me groups [4b].

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confidence: 87%

Section: Methodsmentioning

confidence: 74%

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Synthesis and Properties of Novel (Tricarbonyl)(heptalene)chromium Complexes

Ochertyanova

Hansen

Ustynyuk

2002

HCA

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“…Thermally induced rearrangements have been previously detected in many π complexes, e.g. in monosubstituted [(naphthalene)Cr(CO) 3 ] [64Ϫ66] and monosubstituted [(biphenyl)Cr(CO) 3 ] [67] derivatives. Haptotropic rearrangements reportedly require substantial activation energies, except in the presence of a coordinating solvent.…”

Section: Vtmentioning

confidence: 99%

Synthesis, Structural and Spectroscopic Characterization of Four [(η⁶‐PAH)Cr(CO)₃] Complexes (PAH = Pyrene, Perylene, Chrysene, 1,2‐Benzanthracene)

et al. 2004

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The thermal reaction of hexacarbonylchromium with the polycyclic aromatic hydrocarbons (PAHs) pyrene, perylene, chrysene and 1,2‐benzanthracene has afforded four organometallic complexes of the type [(η6‐PAH)Cr(CO)3], whose unprecedented structures were obtained by single‐crystal X‐ray analysis. The topology of the coordination of the Cr(CO)3 fragment and its asymmetry with respect to the coordinating ring may depend on the opportunity to maintain the maximum aromaticity of the complexed ligand. DFT calculations, 1H NMR, FT‐IR and Raman spectroscopy have been used to elucidate the type of interaction between the PAH ligand and the carbonylmetal moiety, giving insight into the ligand‐to‐metal donor capacity and the intra‐ and intermolecular interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…Such processes consist of the shifting, from one ring to another one, of the ML n organometallic groups along the plane of the carbo- [21] or heterocyclic [22] PALs. A few examples of η It should be noted that usually IRHRs occur in complexes of PALs which do not contain heteroatoms (such as naphthalene [23] or biphenylene [24]), and only little is known about η 6 η 6 -IRHR in fluorene-like compounds containing ligands with at least one heteroatom in the five-membered ring (such as dibenzothiophene [22] or carbazole derivatives [25]). According to density functional theory (DFT) calculations [21], these rearrangements proceed via the ligand periphery and direct heteroatom participation was not found.…”

Section: Introductionmentioning

confidence: 99%

Thermally induced inter-ring haptotropic rearrangements in π-complexes of molybdenum with nitrogen containing polyaromatic heterocycles: A DFT study

Fetisov

Gloriozov

Nechaev

et al. 2017

Journal of Organometallic Chemistry

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Regioselective synthesis of π-complexes of substituted polycyclic aromatic compounds. Experimental (NMR) and theoretical (DFT) studies of η6,η6-haptotropic rearrangements in naphthalenechromiumtricarbonyl complexes

Cited by 52 publications

References 15 publications

Synthesis and Properties of Novel (Tricarbonyl)(heptalene)chromium Complexes

Synthesis and Properties of Novel (Tricarbonyl)(heptalene)chromium Complexes

Synthesis, Structural and Spectroscopic Characterization of Four [(η⁶‐PAH)Cr(CO)₃] Complexes (PAH = Pyrene, Perylene, Chrysene, 1,2‐Benzanthracene)

Thermally induced inter-ring haptotropic rearrangements in π-complexes of molybdenum with nitrogen containing polyaromatic heterocycles: A DFT study

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Regioselective synthesis of π-complexes of substituted polycyclic aromatic compounds. Experimental (NMR) and theoretical (DFT) studies of η6,η6-haptotropic rearrangements in naphthalenechromiumtricarbonyl complexes

Cited by 52 publications

References 15 publications

Synthesis and Properties of Novel (Tricarbonyl)(heptalene)chromium Complexes

Synthesis and Properties of Novel (Tricarbonyl)(heptalene)chromium Complexes

Synthesis, Structural and Spectroscopic Characterization of Four [(η6‐PAH)Cr(CO)3] Complexes (PAH = Pyrene, Perylene, Chrysene, 1,2‐Benzanthracene)

Thermally induced inter-ring haptotropic rearrangements in π-complexes of molybdenum with nitrogen containing polyaromatic heterocycles: A DFT study

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Synthesis, Structural and Spectroscopic Characterization of Four [(η⁶‐PAH)Cr(CO)₃] Complexes (PAH = Pyrene, Perylene, Chrysene, 1,2‐Benzanthracene)