Showing papers on "Norbornadiene published in 1971"
TL;DR: In this paper, a concerted cycloaddition involving an orthogonal approach of the ketene and olefin in accordance with Woodward and Hoffmann's suggestion was proposed.
122 citations
TL;DR: The structure of norbornane and norbornadiene in the gas phase has been investigated by electron diffraction as mentioned in this paper, and the results show that the structure is similar to each other except for the C2-C3 bond distances.
Abstract: The structures of norbornane and norbornadiene in the gas phase have been investigated by electron diffraction. For the most probable models the rg bond lengths and the bond angles (based on the rα structure) with estimated limits of error are as follows: For norbornadiene: C1–C2=1.5354±0.007 A, C2=C3=1.3432±0.003 A, C1–C7=1.573±0.014 A, ∠C1–C7–C4=94·1±3·0°, and θ (the dihedral angle between the C1–C2–C3–C4 and C4–C5–C6–C1 planes)=115·6±2·2°; For norbornane: C–C(average)=1.5488±0.003 A, C1–C2=1.539±0.012 A, C2–C3=1.557±0.025 A, C1–C7=1.560±0.024 A, ∠C1–C7–C4=93·1±1·7°, and θ=113·1±1·8°. The frame structures of these molecules are similar to each other except for the C2–C3 bond distances. All the C–C–C valence angles are appreciably smaller than the tetrahedral angle (∠C1–C7–C4 in particular). The C1–C7, bridge bonds appear to be longer than the normal C–C single bond. The above structures are compared critically with those reported so far by other investigators. A method for estimation of systematic error...
103 citations
30 citations
22 citations
TL;DR: In this article, α,α′-dimethylstilbene is obtained in the reaction of diphenylacetylene with CH 3 MgBr and L 2 PdCl 2 (L = benzonitrile or norbornadiene), in 65% yield based on the alkyne.
21 citations
20 citations
TL;DR: In this article, the interaction of tin(II) chloride with Pt(π-C 3 H 5 )(PPh 3 ) 2 Cl gives the ionic and covalent complexes, [Pt(πC 3H 5 ),PPh3 ) 2 ] and PtSnCl 3,PPh 2 ] respectively.
19 citations
TL;DR: In this paper, it was shown that the I.m.r. and n.r spectra reveal rapid ligand exchange for the Ph3P-complexes at room temperature.
Abstract: The complexes [(diene)MCl]2(M = Rh, diene = norbornadiene, dicyclopentadiene; M = Ir, diene = cyclo-octa-1,5-diene) react with carboxylate ions to give the carboxylate-bridged complexes [(diene)MO2CR]2. Bridgesplitting reactions with triphenylphosphine and ethylenediamine (en) yield the complexes (diene)M(Ph3P)O2CR or [(diene)Rhen]O2CR, characterised by their i.r. and n.m.r. spectra, the latter revealing rapid ligand exchange for the Ph3P-complexes at room temperature. Reaction with hydrochloric acid regenerates the chloro-complexes; oxidative-addition also occurs with the iridium complexes to give the compounds [(cod)IrHCl2]2 and (cod)Ir(PPh3)HCl2.
17 citations
TL;DR: The photochemical addition of toluene-p-sulphonyl cyanide to hex-1-ene, cyclohexene, and norbornadiene was reported in this article.
Abstract: The photochemical addition of toluene-p-sulphonyl cyanide to hex-1-ene, cyclohexene, and norbornadiene is reported.
10 citations
TL;DR: In this article, the n.m.r. spectra of some of the norbornadiene derivatives have been examined and a controversy over band assignments is resolved, and it is shown that the diene derivatives react with triphenylphosphine to give dimeric products (RCO2C7H8)M(O2CR)PPh3]2 in which the organic ligand has rearranged to a nortricyclene system.
Abstract: The complexes (diene)MCl2(diene = norbornadiene, dicyclopentadiene, M = Pd, Pt; diene = cyclo-octa-1,5-diene, hexa-1,5-diene, M = Pt) react with silver carboxylates, AgO2CR (R = CH3, CH2Cl, CH2F, C6H5), to give in most cases the complexes [(RCO2-alkenyl)MO2CR]2 in which one double bond of the diene has undergone nucleophilic attack. In three cases the monomeric products (diene)Pt(O2CR)2 are obtained (diene = norbornadiene, R = CH2Cl, CH2F; diene = cyclo-octa-1,5-diene, R = CH2F). The n.m.r. spectra of some of the norbornadiene derivatives have been examined and a controversy over band assignments is resolved. The norbornadiene derivatives react with triphenylphosphine to give dimeric products [(RCO2C7H8)M(O2CR)PPh3]2 in which the organic ligand has rearranged to a nortricyclene system.
10 citations
TL;DR: Some thermal, probably concerted, rearrangements of norbornadiene and hexamethyl Dewar benzene monoepoxides are described and the influence of rhodium(I) complexes on these rearrangement is reported and discussed in this article.
Abstract: Some thermal, probably concerted, rearrangements of norbornadiene and hexamethyl Dewar benzene monoepoxides are described and the influence of rhodium(I) complexes on these rearrangements is reported and discussed.
TL;DR: In this paper, the addition of dimethyl phosphonate to norbornadiene was found to give four main compounds 2, 3, 4, and 5 whose structures have been demonstrated by chemical and spectroscopical methods.
Abstract: Radical addition of dimethyl phosphonate to norbornadiene was found to give four main compounds 2, 3, 4, and 5 whose structures have been demonstrated by chemical and spectroscopical methods. Particularly noteworthy is the formation of norbornene phosphonate derivatives in addition to the nortricyclene derivatives.
TL;DR: In this article, a series of metal carboxylate complexes with general formula [(carboxycyclo-enyl)M-(OCOR)]2 from the reaction of (diene)MCl2 with the appropriate carboxylic acid is described.
Abstract: The preparation of a series of (diene)metal carboxylate complexes with general formula [(carboxycyclo-enyl)M-(OCOR)]2 from the reaction of (diene)MCl2(diene = cyclo-octa-1,5-diene, norbornadiene, cyclo-octatetraene, dicyclopentadiene, and tetraphenylcyclobutadiene; M = Pd, Pt; R = But, Me, Ph, CH2Cl, CHCl2, CCl3, CF3) with the appropriate carboxylic acid is described. The complexes are considered to be dimeric with carboxylate bridges and with the carboxycyclo-ene ligand linked to the metal by both a σ and an olefinic bond. Exchange equilibria involving the carboxylates have been examined using 1H and 19F n.m.r. The platinum trifluoroacetates appear to exist in monomer–dimer equilibrium. Thermodynamic parameters for the exchange of trifluoroacetic acid for other carboxylate moieties in chloroform solution have been obtained, and indicate that formation of M–C bond is facilitated by electropositive substituents attached to the double bond. Complex formation generally appears to be dominated by the tendency toward M–C σ bond formation in this system.
TL;DR: In this paper, a 2:1 adduct of diphenylacetylene and norbornadiene was obtained for 1,2,3,4,4-tetraphenylbenzene, p-terphenyl, and p-phenyl.
Abstract: Irradiation of diphenylacetylene and norbornadiene gives 1,2,3,4-tetraphenylbenzene, p-terphenyl, and a 2:1 adduct of norbornadiene and diphenylacetylene.
TL;DR: The NMR spectra of the cycloaddition adducts between tetracyanoethylene oxide (TCNEO) and norbornadiene derivatives have been studied in this paper.
Abstract: The NMR spectra of the cycloaddition adducts between tetracyanoethylene oxide (TCNEO) and norbornadiene derivatives have been studied. It was shown that there was significant long-range coupling between 7-anti and endo hydrogens in the adducts and that this long-range coupling was solvent dependent. Based on the present study it is concluded that the long-range coupling between endo and anti hydrogens can be as high as 4·1 Hz when an electronegative substituent is attached to the carbon which bears endo hydrogen.