Conversion of Methyl Ketones into Terminal Acetylenes: Ethynylferrocene

Polin, Johann; Schottenberger, Herwig

doi:10.1002/0471264180.os073.27

Cited by 49 publications

(57 citation statements)

References 10 publications

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“…Single-crystal X-ray structure determinations were performed for ligands 1 a ± d, and two representative molecular structures are shown in Figure 1 and Figure 2. Bond lengths [8]: N(1)ÀC(23) 133.5 (5), N(1)ÀC(24) 134.5 (5), N(2)ÀC (26) 132.8 (6), N(2)ÀC(30) 134.1 (6) [8] for this molecule: N(1)ÀC (21) 136.8 (9), N(1)ÀC(22) 135.2 (8), N(2)ÀC (24) 135.3 (9), N(2)ÀC(28) 128.2 (12), N(3)ÀC(29) 130.2 (9), N(3)ÀC (33) 135.3(9), C(10)ÀC(11) 142.7(12), C(11)ÀC(12) 118.9(12), C(12)ÀC (13) 146.4(10), C(16)ÀC (19) and angles are generally unexceptional. The acetylene groups are almost linear with CC distances of about 119 pm.…”

Section: Introductionmentioning

confidence: 97%

“…Standard protocols [7] could be applied and afforded the coupling products in good yields. Ligands 1 a and 1 b were obtained from the reaction of 4'-(trifluoromethylsulfonyloxy)-2,2':6',2''-terpyridine [8] (2 a) with ethynylferrocene [9] (3 a) and ethynyloctamethylferrocene [10] (3 b), respectively. Ligands 1 c and 1 d were prepared analogously from 4'-(4-bromophenyl)-2,2':6',2''-terpyridine (2 b).…”

Section: Introductionmentioning

confidence: 99%

“…The bite angle of 1 a is about 1518 (N(1)-Zn(1)-N(3) 150.56 (9), N(4)-Zn(1)-N(6) 150.77(9)8). Coordination to zinc has no major effect on the bond parameters of 1 a.…”

Section: Introductionmentioning

confidence: 99%

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Ferrocenyl‐Functionalised Terpyridines and Their Transition‐Metal Complexes: Syntheses, Structures and Spectroscopic and Electrochemical Properties

Siemeling

Brüggen

Vorfeld

et al. 2003

Chemistry A European J

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Terpyridine ligands of the type Fc'-X-tpy (Fc'=ferrocenyl or octamethylferrocenyl, X=rigid spacer, tpy'=4'-substituted 2,2':6',2''-terpyridine) were prepared, crystallographically characterised and used for the synthesis of di- and trinuclear bis(terpyridine) complexes of RuII, FeII and ZnII. Donor-sensitiser dyads and triads based on RuII were thoroughly investigated by (spectro)electrochemistry, UV/Vis, transient absorption and luminescence spectroscopy, and an energy level scheme was derived on the basis of the data collected. Intramolecular quenching of the photoexcited RuII complexes by the redox-active Fc' groups can occur reductively and by energy transfer. Both the redox potential of the donor Fc' and the nature of the spacer X have a decisive influence on excited-state lifetimes and emission properties of the complexes. Some of the compounds show room-temperature luminescence, which is unprecedented for ferrocenyl-functionalised compounds of this kind.

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Ferrocenyl‐Functionalised Terpyridines and Their Transition‐Metal Complexes: Syntheses, Structures and Spectroscopic and Electrochemical Properties

Siemeling

Brüggen

Vorfeld

et al. 2003

Chemistry A European J

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“…Co-ordination of 1 9 and of the alkynes PhCCC 6 H 4 -4-R (R = NO 2 and CN) 10 to [Ru 3 (CO) 12 ] to produce [Ru 3 (µ 3 -η 2 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) and the analogous clusters 4 and 5, respectively, (see Scheme) was carried out as described previously for other RCCR' (R =R' = H, Ph (3), Me and R = H, R' =Ph). P NMR spectra of the unsymmetrical derivatives 2 and 4-5 the dppm phosphorus nuclei appear as two doublets (J P-P 130Hz) whose chemical shift difference decreases with the decreasing electronic asymmetry of the co-ordinated alkyne (2>5>4).…”

Section: Resultsmentioning

confidence: 99%

Electronic interactions in [Ru3(mu3-R² CCC6H4-4-R¹)(mu -dppm)(mu-CO) (CO)7] (R¹ = NO2 and R² = Fc; R¹ = NO2, CN and R² = Ph)

Rosseto¹,

Torres²,

Stein³

et al. 2003

J. Braz. Chem. Soc.

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A coordenação de FcCCC 6 H 4 -4-NO 2 (1) a uma carbonila polinucleada (cluster) de rutênio resultou na formação de [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2). Os voltamogramas cíclicos destes compostos e dos clusters análogos [Ru 3 (µ 3 -η 2 -C 6 H 5 CCC 6 H 4 -4-R)(µ-dppm)(µ-CO)(CO) 7 ] (R= H, 3; CN, 4; NO 2 , 5) permitiram avaliar as comunicações eletrônicas entre os diferentes sítios de oxi-redução (grupos ferrocenil e -NO 2 e o fragmento Ru 3 ) e analisar as capacidades relativas doadora-receptora de cada um dos três centros de oxi-redução que compõem 2. Além disto, a inércia de 2, em comparação com os clusters 3-5, os quais sofrem fácil perda de CO, foi atribuída à interação entre o grupo ferrocenil e a base metálica.The co-ordination of FcCCC 6 H 4 -4-NO 2 (1) to a ruthenium carbonyl cluster to yield [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) is reported. The cyclic voltammograms of these compounds and of the analogous clusters [Ru 3 (µ 3 -η 2 -C 6 H 5 CCC 6 H 4 -4-R)(µ-dppm)(µ-CO)(CO) 7 ] (R= H, 3; CN, 4; NO 2 , 5) allowed an evaluation of the electronic communications between the different redox sites (ferrocenyl and -NO 2 groups, and Ru 3 moiety) and an analysis of the relative electron donor-acceptor capabilities of each of the three redox centres that compose 2. Furthermore, the inertness of 2, compared with clusters 3-5 which loose CO readily was attributed to the interaction between the ferrocenyl group and the metallic frame.Keywords: ruthenium cluster, ferrocene, alkyne, cyclic voltammetry IntroductionStudies of electronic interactions in systems containing multiple redox-active centres are of fundamental importance in the development of molecular-based electronic devices.1 Alkynes can be an elegant option in the search of systems containing multi-redox sites, once they can serve as conjugated bridges between groups of different electronic densities.2 In addition, they are remarkably versatile in their co-ordinating abilities to different metals (σ or π-fashion), that can result in the generation of novel mono or polynuclear metal complexes with attractive properties.3 Compounds derived from ferrocene have been extensively investigated for materials science 4 due to their low cost, stability and interesting redox properties, and can be used in molecular ferromagnets, molecular sensors, electrochemical agents, liquid crystals and non-linear optical materials. 5The aim of this work was to combine the electronic properties of alkynes, the ferrocenyl fragment and carbonyl clusters to build a new supramolecular compound containing various redox sites. Co-ordination of the ferrocenylalkyne FcCCC 6 H 4 -4-NO 2 (1) to a ruthenium carbonyl cluster to produce [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) was therefore investigated. In cluster 2, the ferrocenyl fragment can act as an electron donor in charge-transfer processes, 6 the -NO 2 group as an electron acceptor 7 and the ruthenium moiety as a reservoir of electrons, depending on the co-ordinated ligands...

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“…Fc-B(OH) 2 (1) [18], I-1-C 6 H 3 (CH 2 NMe 2 ) 2 -3,5 (2) [19], Fc-C"CH (4) [20] [24] were prepared the following published procedures. All other chemicals were commercially available and were used as received.…”

Section: General Remarksmentioning

confidence: 99%

Heterobimetallic Fe–Pd and Fe–Pt NCN pincer complexes (NCN=[C6H2(CH2NMe2)2-2,6]−)

Köcher

Lutz

Spek

et al. 2006

Inorganica Chimica Acta

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The meta-diaminoaryl ferrocenes Fc-NCN-H (3) and Fc-C"C-NCN-H (5) (Fc = (g 5 -C 5 H 5 )(g 5 -C 5 H 4 )Fe, NCN-H = C 6 H 3 (CH 2 NMe 2 ) 2 -3,5) can be used as precursors in the preparation of heterobimetallic transition metal complexes of structural type Fc-NCN-MX (NCN = [C 6 H 2 (CH 2 NMe 2 ) 2 -2,6] À ; MX = PdCl (7), PtCl (8), PtI (9)) and Fc-C"C-NCN-MX (MX = PdCl (11), PdI (12), PtCl (13)), respectively. They are accessible by applying different synthesis procedures, including oxidative addition and metallation-transmetallation processes.Cyclovoltammetric studies show that the ferrocene moieties in 3, 5, 7-9 and 11-13 can reversibly be oxidised. The potential of the Fe(II)/Fe(III) redox couple decreases with increasing electron density at the NCN pincer unit. The use of 8 as a possible (electro)chemical sensor in the detection of SO 2 is discussed as well.The solid-state structures of 8 and 13 are reported. The crystals of 8 contain two molecules of 8 in the asymmetric unit. The plane of the C 6 H 2 moiety is with 27.2(3)°and 38.2(3)°tilted towards the C 5 H 4 entity, while in 13 an angle of 45.9(3)°can be found. The d 8 -electron configured platinum atoms possess a somewhat distorted square-planar surrounding, setup by two Me 2 NCH 2 ortho-substituents, the NCN C ipso carbon atom and the chloride ligand.

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Conversion of Methyl Ketones into Terminal Acetylenes: Ethynylferrocene

Cited by 49 publications

References 10 publications

Ferrocenyl‐Functionalised Terpyridines and Their Transition‐Metal Complexes: Syntheses, Structures and Spectroscopic and Electrochemical Properties

Ferrocenyl‐Functionalised Terpyridines and Their Transition‐Metal Complexes: Syntheses, Structures and Spectroscopic and Electrochemical Properties

Electronic interactions in [Ru3(mu3-R² CCC6H4-4-R¹)(mu -dppm)(mu-CO) (CO)7] (R¹ = NO2 and R² = Fc; R¹ = NO2, CN and R² = Ph)

Heterobimetallic Fe–Pd and Fe–Pt NCN pincer complexes (NCN=[C6H2(CH2NMe2)2-2,6]−)

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