Condensation of aldehydes with .mu.-alkylidyne diiron complexes: a new synthesis of .mu.-vinylcarbyne complexes

Casey, Charles P.; Konings, Mark S.; Palermo, Robert E.; Colborn, Robert E.

doi:10.1021/ja00304a057

Cited by 28 publications

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“…The Fe 2 (η-C 5 H 5 ) 2 (CO) 2 (µ-CO)(µ-C) moiety has a cis structure with dimensions similar to those found in other µ-vinylcarbyne cations. [22,38,39] The ϪCHϭ CHϪCHϭC(Cl)Ϫ π-bridge linker displays all-(E) geometry with C15ϪC16 and C17ϪC18 bond lengths of 1.359(5) and 1.356(5) Å respectively, which are rather long for C sp 2 ϪC sp 2 double bonds. Furthermore, there is a shortening of the C sp 2 ϪC sp 2 single bonds towards the diiron terminus [C14ϪC15 ϭ 1.414(5), C16ϪC17 ϭ 1.424 (9), and C18ϪC19 ϭ 1.447(9) Å ], which is evidence for the delocalisation of the positive charge into the vinylcarbyne system and particularly through the first double bond in the solid state.…”

Section: C؊ch‫؍‬ch؊ch‫؍‬c(cl)؊fc)][bf 4 ] (21)mentioning

confidence: 99%

Structure−Property Dependence of the First Hyperpolarisabilities of Organometallic Merocyanines Based on the μ-Vinylcarbynediiron Acceptor and Ferrocene Donor

Farrell

Manning

Murphy

et al. 2001

Eur. J. Inorg. Chem.

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In order to investigate the structure−property relationship of nonlinear optical materials, a series of organometallic chromophores were synthesised utilising the [Fe 2 (η-C 5 H 5 ) 2 (CO) 2 (µ-CO)(µ-C−)] + electron-accepting moiety and the ferrocenyl group, Fc, as the electron donor. The π-linker between these two termini was systematically modified and the mutual electronic communication between them was determined using IR, NMR, and electronic absorption spectroscopy. An X-ray structure determination of [Fe 2 (η-C 5 H 5 ) 2 (CO) 2 (µ-CO)(µ-C−CH=CH−CH=C(Cl)−Fc)][BF 4 ] confirmed the strong electronic interaction between the donor and the acceptor with reduced π-bridge bond-length alternation. The nonlinear optical properties of these complexes were examined using the hyper Rayleigh scattering technique. The experimental first hyperpolarisabilities are some of the highest obtained for ferrocenyl chromophores and, significantly, no enhancement

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Section: C؊ch‫؍‬ch؊ch‫؍‬c(cl)؊fc)][bf 4 ] (21)mentioning

confidence: 99%

Structure−Property Dependence of the First Hyperpolarisabilities of Organometallic Merocyanines Based on the μ-Vinylcarbynediiron Acceptor and Ferrocene Donor

Farrell

Manning

Murphy

et al. 2001

Eur. J. Inorg. Chem.

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Synthesis and Properties of a Novel Series of Organometallic Merocyanines Combining the Potent Electron-Donating [(CpFeCO)2(μ-CO)(μ-C=CH−)] Fragment with Tropylium-Type Acceptors

Farrell¹,

Manning²,

Mitchell³

et al. 2002

Eur. J. Inorg. Chem.

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The potent electron‐donating group [(CpFeCO)2(µ‐CO)(µ‐C=CH−)] was combined with different tropylium‐based acceptors yielding the push‐pull complexes [(CpFeCO)2(µ‐CO)(µ‐C=CH−CH=A)][BF4] where =A represents [=CH−(η7‐C7H6)Cr(CO)3]+ (5), [={C10H7}]+ (azulenylium) (7) [={C10H4Me2iPr}]+ (guaiazulenylium) (8). Crystal structures of the precursor complexes [(CpFeCO)2(µ‐CO)(µ‐C=CH−CH=CH−C7H7)] (3), [(CpFeCO)2(µ‐CO){µ‐C=CH−CH=CH−(η6‐C7H7)Cr(CO)3}] (4) and the push‐pull derivative 5 are presented. Whereas complexes 3 and 4 demonstrate localised carbon−carbon double and single bonds in the π‐bridge between the diiron moiety and the seven‐membered ring a small but distinct π‐bond delocalisation can be observed in the π‐linker of the cationic derivative 5. From the NMR spectroscopic results a correlation between the 13C NMR shift of the bridging carbon atom µ‐C of the diiron unit and the coupling constant J(1H‐1H) of the β‐ and γ‐protons of the π‐bridge was found. This correlation indicates an increased π‐bond delocalisation throughout the conjugated bridge with respect to the electron‐accepting capability in the order tricarbonyl(η7‐cycloheptatrienylium)chromium < guaiazulenylium < azulenylium implying a predominantly charge‐delocalised form in the case of the azulenylium complex 7. Considerably large first hyperpolarisabilities β were determined for 5 and 8 by means of hyper‐Rayleigh scattering. Based on the two‐level model β0 values were calculated and related to the bond‐length alternation in the π‐linker. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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The synthesis and spectroscopic properties of organometallic cyanine analogues

1992

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Organometallic compounds are receiving attention as potential second-order and third-order nonlinear optical (NLO) materials.[' -71 Experimental and theoretical studies on hyperpolarizabilities indicate that molecules with large transition dipole moments and small energy gaps are, in general, likely candidates for NLO materials.[*] Thus, as part of our on going program to develop new chromophores, we sought to design organometallic compounds with these properties. Many organometallic complexes exhibit metal to ligand charge transfer (MLCT) bands. However, these bands often exhibit only moderate extinction coefficients in the range of 1000 -20000 M -cm-' which may be limited by relatively weak coupling between the metal and the ligand."' We believe organometallic compounds could be useful in nonlinear optics[*] if the electronic coupling between the transition metal and the organic fragment can be optimized, thereby resulting in stronger optical transitions.

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Condensation of aldehydes with .mu.-alkylidyne diiron complexes: a new synthesis of .mu.-vinylcarbyne complexes

Cited by 28 publications

References 0 publications

Structure−Property Dependence of the First Hyperpolarisabilities of Organometallic Merocyanines Based on the μ-Vinylcarbynediiron Acceptor and Ferrocene Donor

Structure−Property Dependence of the First Hyperpolarisabilities of Organometallic Merocyanines Based on the μ-Vinylcarbynediiron Acceptor and Ferrocene Donor

Synthesis and Properties of a Novel Series of Organometallic Merocyanines Combining the Potent Electron-Donating [(CpFeCO)2(μ-CO)(μ-C=CH−)] Fragment with Tropylium-Type Acceptors

The synthesis and spectroscopic properties of organometallic cyanine analogues

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