Chromium tricarbonyl complexes with biphenylene as η6 ligand: synthesis, structure, dynamic behaviour in solid state and thermal η6,η6-haptotropic rearrangements. Experimental (NMR) and theoretical (DFT) studies

Oprunenko, Yuri F.; Gloriozov, I. P.; Lyssenko, Konstantin А.; Malyugina, S. G.; Mityuk, D. Yu.; Mstislavsky, V. I.; Günther, Harald; Firks, Gero von; Ebener, Michael

doi:10.1016/s0022-328x(02)01426-2

Cited by 38 publications

(49 citation statements)

References 36 publications

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“…[103] Indeed, the 13 C CPMAS data of the crystalline compound confirm that in the solid state at room temperature the rotation of the Cr(CO) 3 -group around the Cr-ligand axis stops. On the other hand the 13 C MAS spectrum of the complex supported on silica gel is completely resolved showing very narrow signals (Ͻ 15 Hz) indicating a considerable mobility of the absorbed molecules able to average the strong dipolar interaction.…”

Section: Solid-state Mobility Vs Solid-state Reactivitymentioning

confidence: 78%

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Solid‐State NMR Investigation of Ligand Mobility and Reactivity in Transition Metal Complexes

Chierotti

Gobetto

2009

Eur J Inorg Chem

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Solid-state NMR spectroscopy represents a powerful tool to access information on chemical structure, dynamics and reactivity at molecular level on solid compounds and materials. Transition metal complexes represent an unrestricted source of examples for solid-state dynamics and reactivity due to the presence of highly mobile groups, very reactive ligands and the possibility of expanding the coordination sphere. The key question of the influence of the mobility on the reactivity of a system is the occasion for presenting several selected examples of solid-state dynamics and reactivity of transition metal complexes. Although only few unambiguous examples

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Section: Solid-state Mobility Vs Solid-state Reactivitymentioning

confidence: 78%

“…[103] and monitored by 13 C CPMAS, has been shown to obey a first-order Avrami-Erofe'ev rate law typical of a nucleation and growth mechanism. Notably, the observed irreversibility of this process was attributed to local differences of CO fluxional behaviour in both the cis and trans isomers.…”

Section: Solid-state Mobility Vs Solid-state Reactivitymentioning

confidence: 99%

Solid‐State NMR Investigation of Ligand Mobility and Reactivity in Transition Metal Complexes

Chierotti

Gobetto

2009

Eur J Inorg Chem

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“…[16] The metal slides from the (near)center of one benzene ring to the quaternary (fourmembered) ring carbon to reach a distorted trimethylenemethane maximum, and then proceeds to the edge of the bridging cyclobutadiene bond. This species represents a minimum on the potential energy curve and adopts an h 2 -like complexed cyclobutadiene topology ("quasi-h 4 "), from which it continues by the microscopic reverse on to the other benzene nucleus.…”

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confidence: 99%

Photo–Thermal Haptotropism in Cyclopentadienylcobalt Complexes of Linear Phenylenes: Intercyclobutadiene Metal Migration

et al. 2009

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An attractive strategy for achieving solar-thermal energy conversion is to harvest sunlight in the form of activated chemical bonds through photoisomerization of a suitable molecule that can release, on demand, such stored and transportable energy by thermal reversal to its original form.[1] When such reversible isomerizations entail significant topological alterations, they provide blueprints for eliciting further functions, for example in switches, machines, datastorage, sensors, and other devices. [1,2] Because of their expanded tunability and generally favourable electronic absorption regimes, organometallic complexes are advantageous in this respect, yet have remained relatively unexplored.[3] Among them, topologically simplest are metallohaptotropic arrays in which a single metal moiety photomigrates, thermally reversibly, to a higher-energy position along a fused p framework, without the assistance of additives.[4] Only two such systems are known, [Mo(PMe 3 ) 3 ] complexes of indole and quinazoline, discovered as part of a study focusing on catalytic hydrogenations of heterocycles. [5] We report 1) the photothermal reversibility of {CpCo} complexes of linear phenylenes [6] by a novel mode of haptotropism, namely, h 4 :h 4 from one cyclobutadiene ring to another (Scheme 1); 2) the first X-ray structures of metalated linear phenylenes, illustrating the aromatization of the ligand on complexation; 3) mechanistic aspects of the isomerization cycles; and 4) a DFT study providing a detailed picture of how the {CpCo} unit moves across the arene separating the two cyclobutadiene rings.The new complexes, 2, 5, and 6-8, were made from the respective 2,3,6,9-tetraethynyl linear [3]phenylene, 1,2,4,5-tetraethynylbenzene, and 2,3-diethynylbiphenylene ([D 2 ] for 8) synthons and their cocyclization with bis(trimethylsilyl)-acetylene (BTMSA) in the presence of stoichiometric [CpCo(CO) 2 ] (MeCp for 7), a strategy employed previously Scheme 1. Photo-thermal cycles of CpCo-phenylene complexes.

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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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Chromium tricarbonyl complexes with biphenylene as η6 ligand: synthesis, structure, dynamic behaviour in solid state and thermal η6,η6-haptotropic rearrangements. Experimental (NMR) and theoretical (DFT) studies

Cited by 38 publications

References 36 publications

Solid‐State NMR Investigation of Ligand Mobility and Reactivity in Transition Metal Complexes

Solid‐State NMR Investigation of Ligand Mobility and Reactivity in Transition Metal Complexes

Photo–Thermal Haptotropism in Cyclopentadienylcobalt Complexes of Linear Phenylenes: Intercyclobutadiene Metal Migration

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

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