Showing papers on "Norbornadiene published in 1977"
TL;DR: In this article, the advantages of isolating the photosensitizer to the photochemical reactor stage of a photochemical solar energy storage device have been discussed, and efficient sensitization by polymer bound photosensizers demonstrates the feasibility of this approach.
74 citations
TL;DR: A detailed investigation of the photoassisted valence isomerization of norbornadiene (NBD) to quadricyclene (Q) in the presence of copper(I) salts is reported in this article.
Abstract: A detailed investigation of the photoassisted valence isomerization of norbornadiene (NBD) to quadricyclene (Q) in the presence of copper(I) salts is reported. In the prototypal cuprous chloride-norbornadiene system, spectral evidence indicates that a 1 : 1 ClCu-NBD ..pi.. complex is present in solution and is, in fact, the photoactive species. Quantum yield data obtained in several solvents and at different initial NBD concentrations support this premise. The photoreaction is thought to originate via population of an olefin-metal charge-transfer state of the complex. Possible pathways by which this excited state yields Q are considered. The absence of NBD photodimerization products suggests that Cu(I) salts containing strongly binding anions have little tendency to coordinate more than one NBD molecule.
64 citations
52 citations
47 citations
TL;DR: In this paper, the first definitive evidence for a cis addition of Pd-R to a coordinated double bond was presented, which was later confirmed in the case of dichloro-μ4-norbornadieneplatinum.
45 citations
41 citations
TL;DR: In this paper, a study was made of the norbornadiene (NBD) to quadricyclene (Q) conversion in the presence of Cu(P(CH/sub 6/H/sub 5)/sub 3/)/sub 2/BH/Sub 4/, and Cu(diphos)BH /sub 4/ (Diphos is 1,2-bis(diphenylphosphino)ethane).
Abstract: A study was made of the norbornadiene (NBD) to quadricyclene (Q) conversion in the presence of Cu(P(CH/sub 6/H/sub 5/)/sub 3/)/sub 2/BH/sub 4/, Cu(P(C/sub 6/H/sub 5/)/sub 2/(CH/sub 3/))/sub 3/BH/sub 4/, and Cu(diphos)BH/sub 4/ (diphos is 1,2-bis(diphenyl-phosphino)ethane). The first two compounds were approximately 60 to 90 times more effective than the latter compound in sensitizing the production of Q. Furthermore, the mechanism of sensitization appears to be fundamentally different from that involving CuX salts (where X is Cl, Br, I, or C/sub 2/H/sub 3/O/sub 2/). (JSR)
35 citations
TL;DR: In this article, the labile acetone ligand from [Rh(diene)(PPh3)(acetone)]A (diene) = 1,5-cyclooctadiene (COD), norbornadiene(NBD); A(PF6−, SbF6−) allows facile coordination of dialkyl or alkyl ar...
Abstract: Displacement of the labile acetone ligand from [Rh(diene)(PPh3)(acetone)]A (diene = 1,5-cyclooctadiene (COD), norbornadiene (NBD); A = PF6−, SbF6−) allows facile coordination of dialkyl or alkyl ar...
34 citations
TL;DR: In this paper, a solar energy storage system based upon the valence isomerization of norbornadiene to quadricyclene has been proposed, which has several attractive features, including high specific energy storage capacity, kinetic stability of the energy rich photoproduct in the absence of suitable catalysts, and relatively inexpensive reactants.
29 citations
TL;DR: Tris(triphenylphosphine)tetramethylenenickel(II) and biscyclopentadienyltetramerethylenetitanium, prepared from the reaction of a 1,4-dilithiobutane and the transition metal dihalides react with olefins to produce substituted metallacyclopentanes as discussed by the authors.
Abstract: Tris(triphenylphosphine)tetramethylenenickel(II) and biscyclopentadienyltetramethylenetitanium, prepared from the reaction of a 1,4-dilithiobutane and the transition metal dihalides react with olefins to produce substituted metallacyclopentanes; the stereochemistry and substitution pattern of the metallocycles formed from propene, octa-1,7-diene, and norbornadiene has been determined.
29 citations
TL;DR: The 1,3-dipolar cycloadditions of phenylglyoxylonitrile oxide, benzonitrile-N-phenylimine, or N-phenyl-C-p-nitrophenylnitrone to norbornadiene, 2,3dicyanonorbornadienes, and 2, 3-bis(methoxycarbonyl...
Abstract: The 1,3-dipolar cycloadditions of phenylglyoxylonitrile oxide, benzonitrile-N-phenylimine, or N-phenyl-C-p-nitrophenylnitrone to norbornadiene, 2,3-dicyanonorbornadiene, and 2,3-bis(methoxycarbonyl...
TL;DR: In this paper, NMR spectroscopy was used to determine the nature of the species present in catalytically active solutions prepared by treating [RhCl(C 2 H 4 ) 2 ] 2 with diphosphines and [Rh(norbornadiene)diphosphine]BF 4 with hydrogen.
TL;DR: In this paper, the authors used chiral phosphines under hydrogen as catalysts for the homogeneous hydrogenation of Schiff bases at 30-80° and 1-70 bars.
Abstract: Complexes formed from [Rh(norbornadiene)Cl]2 and tertiary phosphines under hydrogen are active catalysts for the homogeneous hydrogenation of Schiff bases at 30–80° and 1-70 bars. Using chiral phosphines some optical induction can be achieved, but the optical yields are rather low.
TL;DR: In this article, a discussion on the mechanism of the chromous chloride promoted addition of N-haloamides to olefins is presented on the basis of the results already reported and some additional evidence.
Abstract: A discussion on the mechanism of the chromous chloride promoted addition of N-haloamides to olefins is presented on the basis of the results already reported and some additional evidence. The mechanism proposed involves a radical chain addition in which the N-haloamide acts as the transfer agent, the termination steps being chromium(II) reduction of the amido radical and chromium(II) reduction of the intermediate adduct radical. The addition of N-chloro- and N-bromoacetamide to norbornadiene is described. The use of chromous chloride to initiate the reaction of N-chloropiperidine with ethyl vinyl ether and cyclohexene led to low yields of addition.
TL;DR: In this paper, the reaction of PF5 and PhPF4 with 2-[bis(trimethylsilyl)amino]-2,2-difluoro-4,4,5,5-5-tetrakis-(trifluormethyl)-1,3,2λ5-dioxaphospholan (1b) ergibt das trifluorphosphorane 2 bzw.
Abstract: Die Reaktion von PF5 bzw. PhPF4 mit 2-[Bis(trimethylsilyl)amino]-2,2-difluor-4,4,5,5-tetrakis-(trifluormethyl)-1,3,2λ5-dioxaphospholan (1b) ergibt das Trifluorphosphoran 2 bzw. 3, das erste stabile Fluorphosphazophosphoran. 2 setzt sich mit Methoxytrimethylsilan zu dem thermisch bestandigen Difluormethoxyphosphoran 4 um, mit Hexamethyldisiloxan entsteht 5, das mit PF5 leicht in 2 umgewandelt werden kann. Diphenyl(trimethylsilyl)phosphin reduziert 2 zu dem cyclischen Fluorphosphit 6, das in (C7H8)Mo(CO)4 (C7H8 = Norbornadien) das Cycloolefin unter Bildung des cis-Komplexes 7 substituiert. Die spektroskopischen Daten werden diskutiert.
Reactions of 2,2,2-Trifluor-4,4,5,5-tetrakis(trifluormethyl)-1,3,2λ5-dioxaphospholane
PF5 and PhPF4 react with 2-[bis(trimethylsilyl)amino]-2,2-difluoro-4,4,5,5-tetrakis (trifluoromethyl)-1,3,2λ5-dioxaphospholane (1b) to yield the trifluorophosphorane 2 or 3, respectively. 3 is the first known example of a stable fluorophosphazophosphorane. 2 reacts with methoxytrimethylsilane to give the thermally stable difluoromethoxyphosphorane4; with hexamethyldisiloxane 5 is obtained. PF5 easily converts 5 into 2. Diphenyl(trimethylsilyl)phosphine reduces 2 to the cyclic fluorophosphite 6, which displaces the coordinated cycloolefin in (C7H8)Mo(CO)4 (C7H8 = norbornadiene) with formation of the cis-complex 7. The spectroscopic data are discussed.
TL;DR: In this article, the voltammetric behavior of chelates of the type [M(chel)L] + (M = Rh, Ir; chel = 2,2′-bipyridine (bipy); 1,10-phenanthroline (phen); L = cis, cis -cycloocta-1,5-diene; norbornadiene and [Rh(chel 2 L] + ) undergo oxidation at the mercury electrode.
TL;DR: In this article, the NMR spectra obtained for the norbornadiene complex Os 3 (CO) 10 (C 7 H 8 ) indicate restricted equilibration of in-plane carbonyls via a triply bridged intermediate.
TL;DR: In this paper, the cyclopentanone was always formed in these reactions and the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, respectively.
Abstract: Photochemical reactions of norbornadiene with substituted acetylenes in the presence of Fe(CO)5 gave various products of different types, depending on the nature of the acetylene. The results are summarized in Table 1. The cyclopentanone 1 was always formed in these reactions. In the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, the cyclopentenones 2 and 5 were formed, respectively. By contrast, propiolic esters produced the cyclohexenones 3 and 4, in which the ester group was attached on the β carbon with respect to the keto group. Plausible mechanisms for the formation of these products are shown in Schemes 7 and 8. The reaction of diphenylacetylene gave the cyclohexendione 7 as well as the cyclopentenone 6. Two enedione products 8 and 9 were obtained from the reaction of phenylacetylene. Compound 9 was converted to the aromatic diacetate 13 by heating with acetic anhydride in pyridine. On irradiation in the presence of Fe(CO)5 norbornene reacted similarly with dimethyl acetylenedicarboxylate and phenylacetylene to give the cyclopentenone 14 and the cyclohexenone 15, respectively. Compound 15, upon heating, isomerized to hydroquinone 16, which on acetylation gave the diacetate 17.
TL;DR: In this article, the Meerwein-Wagner rearrangement occurred only in the case of chlorine or fluorine halosubstituents of β-carbonium ions formed by exo attack of the electrophile.
TL;DR: In this paper, the dimeric η1-ylide palladium complex, [PhMe2P+CH(SiMe3)}Cl2Pd−]2 (I), prepared in 94% yield from (PhCN) 2PdCl2 and PhMe 2PCHSiMe 3, is converted to a new η 1-ylides cyclic diolefin complex, by the abstraction of the chloride anion of I with silver hexafluorophosphate in the presence of 1,5-cycl
TL;DR: The reaction of substituted (difluoroiodo)benzenes with norbornadiene results in four products: 3-exo,5-endo-(2)(49-55%), 3- exo, 5-hexhexene-(3)(15-20%), and 3-hexene(2.2.1) as mentioned in this paper.
Abstract: The reaction of substituted (difluoroiodo)benzenes with norbornadiene results in four products: 3-exo,5-endo-(2)(49–55%), 3-exo,5-exo-(3)(15–20%), and 3-endo,5-endo-difluorotricyclo[2.2.1.0]heptane (4)(6–8%), and 5-exo,7-syn-difluoronorborn-2-ene (5)(18–32%), depending upon the substituent in the benzene ring. The reaction with 1,4-dihydro-1,4-methanonaphthalene results in 2-exo,9-syn-difluoro-1,4-dihydro-1,4-methanonaphthalene.
TL;DR: Cationic nitrosyl compounds obtained by chloride abstraction from [Fe(NO) 2 -Cl] 2 are catalysts for the polymerisation of acrylonitrile and styrene and the dimerisation of norbornadiene as mentioned in this paper.
Patent•
11 Apr 1977
TL;DR: In this article, a ring opening polymer with high yields was obtained by ring-opening polymerization of norbornadiene derivatives, using a catalyst system obtained from a reaction product of an organometallic compound, an oxide of W and/or Mo and a Lewis acid and a reactive group-containing polymer.
Abstract: PURPOSE:To prepare a ring opening polymer with high yields by ring opening polymerization of norbornadiene derivatives, etc. by the use of a catalyst system obtained from a reaction product of an organometallic compound, an oxide of W and/or Mo and a Lewis acid and a reactive group-containing polymer.
TL;DR: The reaction between these two compounds occurred readily by addition of catalytic amount of AgClO4 to give [Pd(CR=CRCH2SCH3)Cl]2 (R= COOCH3).
Abstract: Insertion of RC≡CR (R= COOCH3) or 2,5-norbornadiene into the Pd–C bond of Pd(Ph3P) (CH2SCH3) (OCOCF3) gave the corresponding cis-addition product in good yield. Pd(Ph3P) (CH2SCH3)Cl was unreactive toward RC≡CR (R= COOCH3), however, the reaction between these two compounds occurred readily by addition of catalytic amount of AgClO4 to give [Pd(CR=CRCH2SCH3)Cl]2 (R= COOCH3).
TL;DR: In this article, the exo/endo product ratios for three types of 1,3-dipolar cycloadditions of phenylglyoxylonitrile oxide(1) to 2,3bis(methoxycarbonyl)norbornadiene(2a), norbornadienes, and 2, 3-dicyanonorbornadene decrease with increasing ET value of the non-aromatic polar solvent used.
Abstract: The exo/endo product ratios for three types of 1,3-dipolar cycloadditions of phenylglyoxylonitrile oxide(1) to 2,3-bis(methoxycarbonyl)norbornadiene(2a), norbornadiene, and 2,3-dicyanonorbornadiene decrease with increasing ET value of the non-aromatic polar solvent used. The exo/endo ratio in the reaction of 1 with 2a is larger than unity, but the value of ΔHexo\eweq−ΔHendo\eweq is nevertheless positive. This phenomenon is attributed to the relatively large positive value of ΔSexo\eweq−ΔSendo\eweq, that is, ΔGexo\eweq−ΔGendo\eweq<0 at ordinary temperatures. On the basis of these results, the conditions, under which the exo/endo ratio in the reaction of 1 with 2a is smaller than unity, were determined. The results can be reasonably explained by the assumption that the dipole moment of the endo-form in the transition state is greater than that of the exo-form.
Patent•
10 Feb 1977
TL;DR: In this article, a three component catalystic system of diethylaluminum chloride, ferric acetylacetonate and triphenylphosphino was used for the continuous production of endo-endo stereoisomer of the hexacyclic dimer of norbornadiene.
Abstract: Process involves the continuous production of endo-endo stereoisomer of the hexacyclic dimer of norbornadiene using a three component catalystic system of diethylaluminum chloride, ferric acetylacetonate and triphenylphosphino. Temperature range of reaction is about 100°-200° F and residence time is about 1-10 hours. Process further involves taking a product stream, along with any catalyst and other materials, and treating it to deactivate the catalyst; then separating the desired endo-endo dimer by various means at a temperature below about 500° F to avoid decomposition of iron salts. Unreacted norbornadiene is recycled.
TL;DR: From the hexacarbonyl complexes of chromium, molybdenum, and tungsten via the norbornadiene complexes the compounds cis-M(CO)4[As(CH3)2Cl]2 (1, M = Cr, Mo, W) are formed in good yields as discussed by the authors.
Abstract: Aus den Hexacarbonylkomplexen des Chroms, Molybdans und Wolframs lassen sich uber die Norbornadienkomplexe in guter Ausbeute die Verbindungen cis-M(CO)4[As(CH3)2Cl]2 (1, M = Cr, Mo, W) gewinnen. Diese setzen sich mit aquimolaren Mengen von Carbonylmetallaten zu den arsenverbruckten Zweikernkomplexen M′ As(CH3)2 M(CO)4 As(CH3)2Cl (M′ = Mo(CO)3C5H5, W(CO)3C5H5, Mn(CO)5, Re(CO)5, Co(CO)4) um, die noch die reaktiven Chlordimethylarsin-Liganden tragen. Deren Verwendbarkeit fur weiterfuhrende Synthesen wird durch die Darstellung des Hetero-Dreikernkomplexes (CO)5Mn As(CH3)2 Cr(CO)4 As(CH3)2 Re(CO)5 demonstriert.
Dinuclear Complexes with Chlorodimethylarsine Ligands
From the hexacarbonyl complexes of chromium, molybdenum, and tungsten via the norbornadiene complexes the compounds cis-M(CO)4[As(CH3)2Cl]2 (1, M = Cr, Mo, W) are formed in good yields. These react with equimolar amounts of carbonylmetalates to give arsenic-bridged dinuclear complexes M′ As(CH3)2 M(CO)4 As(CH3)2Cl (M′ = Mo(CO)3C5H5, W(CO)3C5H5, Mn(CO)5, Re(CO)5, Co(CO)4), which still bear the reactive chlorodimethylarsine ligands. The use of these for further syntheses is demonstrated by the preparation of the heterotrinuclear complex (CO)5Mn As(CH3)2 Cr(CO)4 As(CH3)2 Re(CO)5.