Syntheses, structures and electrochemistry of some 1-(η2-allylamino)-1-ferrocenylcarbene complexes of chromium(0), molybdenum(0) and tungsten(0)

Schobert, Rainer; Kempe, Rhett; Schmalz, Thomas; Gmeiner, Alexander

doi:10.1016/j.jorganchem.2005.10.047

Cited by 15 publications

(9 citation statements)

References 38 publications

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“…Particularly, for complexes 2 ( a-b ), we observe the only presence of Z -isomers. This behavior is presumably due to the bulkiness of the Fc residue, which has a steric repulsion with the side-chain, as observed in other ferrocenyl amino carbenes analogues [30]. In the case of 4 ( a-b ) complexes, they exist as mixtures of Z - and E -isomers with regard to the partial C-N double bound, being the isomer E the main specie, in accordance with the literature [31].…”

Section: Resultssupporting

confidence: 80%

Nanostructured Thin Films Obtained from Fischer Aminocarbene Complexes

et al. 2016

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Abstract:The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO) 5 NH(CH 2 ) 15 CH 3 , where R is a ferrocenyl 2(a-b) or a phenyl 4(a-b) group as a donor moiety and a Fischer carbene of chromium (0) or tungsten (0) as an acceptor group, are reported. These four push-pull systems formed Langmuir (L) monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves); Brewster angle microscopic images were also obtained. By using the Langmuir-Blodgett (LB) method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl)(hexadecylamine)methylidene] pentacarbonyl tungsten (0) are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices.

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Section: Resultssupporting

confidence: 80%

Nanostructured Thin Films Obtained from Fischer Aminocarbene Complexes

et al. 2016

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“…The tungsten Fischer carbene complexes 1 -4 were prepared using the classical Fischer carbene synthetic methodology in which W(CO) 6 was reacted with LiR (R = Fc, fc, bfc; Fc = ferrocenyl, fc = ferrocen-1,1'-diyl, bfc = 1',1''-biferrocen-1,1'''diyl) to form the corresponding metal acylate, followed by a subsequent alkylation via addition of methyl trifluoromethanesulfonate (MeOTf) (Scheme 1, Experimental Section). Complex 1 has been previously prepared, 14 but single X-ray diffraction data have not been reported.…”

Section: Resultsmentioning

confidence: 99%

Metal–Metal Interaction in Fischer Carbene Complexes: A Study of Ferrocenyl and Biferrocenyl Tungsten Alkylidene Complexes

et al. 2013

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A series of ferrocenyl (Fc = ferrocenyl; fc = ferrocen-1,1'-diyl) and biferrocenyl (Bfc = 1',1''-biferrocenyl; bfc = 1',1''-biferrocen-1,1'''-diyl) mono-and biscarbene tungsten(0) complexes of the type [(CO) 5 W=C(OMe)R] (1, R = Fc; 3, R = Bfc) and [(CO) 5 W=C(OMe)-R'-(OMe)C=W(CO) 5 ] (2, R' = fc; 4, R' = bfc) were synthesized according to the classical synthetic methodology by reacting W(CO) 6 with LiR (R = Fc, fc, bfc), followed by a subsequent alkylation using methyl trifluoromethanesulfonate. Electrochemical investigations were carried out on these complexes to get a closer insight into the electronic properties of 1 -4. The ferrocenyl and biferrocenyl moieties in 1 -4 show reversible one electron redox events. It was further found that the Fischer carbene unit is reducible in an electrochemical one electron transfer process. For the tungsten carbonyl moieties, irreversible oxidation processes were found. In addition, charge transfer studies were performed on 1 -4 by the use of in situ UV-Vis-NIR and infrared spectroelectrochemical techniques. During the UV-Vis-NIR investigations typical low energy transitions for the mixed-valent biferrocenyl unit were found. A further observed high energy NIR absorption is attributed to a metal-metal charge transfer transition between the tungsten carbonyl fragment and the ferrocenyl/biferrocenyl group in the corresponding oxidized states, which can be described as class II systems according to Robin and Day. This assignment was verified by infrared spectroelectrochemical studies. The electrochemical investigations are supported by DFT calculations. The structural properties of 1 -4 in the solid state were investigated by single-crystal Xray diffraction studies showing no substituent effects on bond lengths and angles. The biferrocenyl derivatives exhibit synconformation of the ferrocenyl and carbene building blocks.

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“…As an extension of this work, the study of 1-ferrocenyl substituted chelated (η 2 -alkene) aminocarbene complexes were expanded to include different alkenyl-substituents, eg. hydroxyl-groups [145]. This was done to further investigate the potential handle on the overall complex reactivity of such η 2 -bonded exometallacyclic ligands.…”

Section: π-Aryl Monocarbene Complexes Viii(a)mentioning

confidence: 99%