Showing papers on "Norbornadiene published in 1985"
TL;DR: In this paper, an outstanding molecular energy storage system A/B composed of a cycle of reactions including a direct sunlight-induced endoergic process and an energy-releasing reverse process was investigated on the basis of new concepts.
144 citations
TL;DR: In this paper, a non-cage-like sequence of at least three coordination sites in the coordination sphere of the propagating species, is proposed to explain the experimental results.
59 citations
58 citations
TL;DR: C 37 H 44 ClFeO 4 P 2 Rh cristallise dans P2 1 /c avec Z=4; affinement jusqu'a R=0,031 as mentioned in this paper.
56 citations
TL;DR: In this article, a general reaction scheme was proposed for the hydrogenation of ketones employing cationic rhodium(I) complexes and a neutral complex, which showed an unusual negative temperature dependence of the reaction rate.
47 citations
TL;DR: In this paper, the authors propose a cristillation dans P2 1 /n avec Z=4; affinement jusqu'a R=0,069.
39 citations
29 citations
TL;DR: In this paper, bidentate heterocyclic chelating ligands (LL) have been used to generate diolefin neutral, ionic or ion-pair type compounds depending on the ligands and/or the ratio employed.
Abstract: Cleavage of [{Rh(diolefin)Cl}2] by bidentate heterocyclic chelating ligands (LL) has been studied, and diolefin neutral, ionic or ion-pair type compounds are formed depending on the ligands and/or the Rh: (LL) ratio employed. When the reactions are performed in media saturated with CO and with Rh: (LL)=2∶1, only carbonylated ion-pair complexes are formed. The diolefin compounds react with tin(II) chloride yielding species containing trichlorostannato-groups. Subsequent reaction with CO leads to displacement of the diolefin and formation of the corresponding dicarbonyl species.
27 citations
26 citations
TL;DR: In this paper, the crystal structures of the complexes [Rh{CPh(NPh)2}(cod)](1) and [Rh2{µ-CPhNPh2}2(tfbb)2](4) have been determined by X-ray diffraction methods.
Abstract: Complexes [{MCl(diolefin)}2](M = Rh or Ir) react with N,N′-diphenylbenzamidinate to yield binuclear [Rh2{µ-CPh(NPh)2}2(diolefin)2][diolefin = norbornadiene (nbd) or tetrafluorobarrelene (tfbb)] or mononuclear [M{CPh(NPh)2}(cod)](cod = cycle-octa-1,5-diene) complexes. The rhodium complexes react with carbon monoxide to give [Rh2{µ-CPh(NPh)2}2(CO)4]. The latter complex undergoes a two-centre oxidative addition with iodine yielding the rhodium(II) complex [Rh2{µ-CPh(NPh)2}2I2(CO)4]. An A-frame compound of formula [Rh2{µ-CPh(NPh)2}(µ-dppm)2(CO)] ClO4(dppm = Ph2PCH2PPh2) has been isolated. Some related mononuclear complexes containing a unidentate benzamidine ligand have also been prepared. The crystal structures of the complexes [Rh{CPh(NPh)2}(cod)](1) and [Rh2{µ-CPh(NPh)2}2(tfbb)2](4) have been determined by X-ray diffraction methods. Complex (1) crystallizes in the monoclinic space group P21/n, with a= 10.315(2), b= 19.507(3), c= 11.429(3)A, β= 103.62(1)°, and Z= 4. Crystals of compound (4) are monoclinic, space group P21/c, with Z= 4 and a unit cell of dimensions a= 21.692(2), b= 12.512(2), c= 19.969(2)A, and β= 107.90(1)°. Both structures were solved by Patterson and Fourier methods and refined by full-matrix least squares to R 0.040 and 0.047, respectively. The structure of (1) is mononuclear with the N,N′-diphenylbenzamidinate acting as a chelating ligand, through the nitrogen atoms. In contrast, complex (4) is binuclear with the benzamidinate ligand bridging two rhodium atoms [ Rh ⋯ Rh 2.982(3)A].
25 citations
TL;DR: In this paper, the authors studied the performance of polysiloxanes containing vinyl and Si-H groups catalyzed by [RhCl(CO)2]2, [RCl(C2H4)2], [RCL[P(C6H5)3]3, and RhCl(acac)3 (1, 5-COD = 1,5-cyklooktadiene, NBD = norbornadiene and acac = acetylacetonate).
Abstract: Vulcanization of silicon rubber compound based on polysiloxanes containing vinyl and Si–H groups catalyzed by [RhCl(CO)2]2, [RhCl(C2H4)2]2, [RhCl(1,5-COD)]2, [RhCl(NBD)]2, RhCl[P(C6H5)3]3, and Rh(acac)3 (1,5-COD = 1,5-cyklooktadiene, NBD = norbornadiene, acac = acetylacetonate) has been studied in dependence on the catalyst, solvent, and reaction conditions. The course of vulcanization as well as the crosslinking density of the vulcanizate and the content of sol indicate that the above catalysts are comparable to and in some cases even better than the widely used hexachloroplatinic acid.
TL;DR: A molybdenum-mediated dimerization of norbornadiene and its 7-t-butoxy derivative gives good yields of products with a cage skeleton, heptacyclo[6.6.0.
Abstract: A molybdenum-mediated dimerization of norbornadiene and its 7-t-butoxy derivative gives good yields of products with a cage skeleton, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane, whose structure has been analysed by X-ray crystallography.
TL;DR: In this article, WBr 2 (CO) 2 (C 7 H 8 ) cristallise dans le systeme monoclinique, groupe P2 1 /n and le compose WBr2 (CO 2 (PPh 3 ) 2 dans the systeme triclinique.
Abstract: Le compose WBr 2 (CO) 2 (C 7 H 8 ) cristallise dans le systeme monoclinique, groupe P2 1 /n et le compose WBr 2 (CO) 2 (PPh 3 ) 2 dans le systeme triclinique, groupe P1. Affinement des structures jusqu'a R=0,032 et 0,064 respectivement. Le premier compose est diamagnetique a geometrie pseudo-octaedrique. Le second possede une geometrie octaedrique tres deformee
TL;DR: The stereochemistry of hydrogenation of a range of unsaturated cyclohexanecarboxylic acids and their esters has been investigated, employing either bis(1,4-diphenylphosphino)butanerhodium or pyridine(tricyclohexylphophosphine)iridium based cationic catalysts in CH 2 Cl 2.
TL;DR: The intramolecular Diels-Alder reaction of a (5′-hexynyl)cyclopentadiene provides a 1,2-tetramethylene-bridged norbornadiene which undergoes selective monohydrogenation followed by ozonolysis to provide the title compounds as mentioned in this paper.
TL;DR: The photoisomerization of 3-(aryicarbamoyl)norbornadiene-2-carboxylic acid 1 to the corresponding quadricyclane derivative 2 in an aqueous alkaline solution was clean and dependent upon the p-substituent of the aryl group as discussed by the authors.
Abstract: Photoisomerization of 3-(aryicarbamoyl)norbornadiene-2-carboxylic acid 1 to the corresponding quadricyclane derivative 2 in an aqueous alkaline solution was clean and dependent upon the p-substituent of the aryl group. The exothermically reversal reaction of 2 to 1 was also clean but independent upon the substituent.
TL;DR: The fraction of incident radiant energy stored in chemical form by the photosensitized isomerization of norbornadiene to quadricyclane has been estimated in this paper, showing that about 8.8% of the total available incident light contained in the region from 300 nm (lower end of the solar spectrum that impinges upon the earth's surface) to 425 nm (approximate absorption threshold of the sensitizers acetophenone and benzophenone; maximum wavelength capable of promoting the reaction under the conditions of this study) can be stored in the chemical bonds
TL;DR: In this article, the coordinating properties of trifluoromethyl elemental compounds Me 2 PP(CF 3 ) 2 and Me 2 AsP(CF3 ) 2 have been studied by the synthesis and spectroscopic investigations (IR, NMR, MS) of their complexes cis -M(CO) 4 L 2 (A ), [(CO] 4 ML] 2 (B ), and [(CO) 5 M] 2 L (C ) (M = Cr, Mo, W).
TL;DR: In this article, the carbon-to-metal bondings of the bis(norbornadiene)dicarbonylmolybdenum complex were examined by 1 H and 13 C NMR, and it was found that the chemical shifts of one double bond on each ligand are located significantly upfield from the other.
TL;DR: In this paper, the Ph2PCH2CH2PPh2(dppe) bridged, bimetallic 10-membered ring complexes (OC)4M1(µ-dppe)-2-M2(CO)4] have been synthesized by treating a complex of type cis-[M1.
Abstract: The Ph2PCH2CH2PPh2(dppe) bridged, bimetallic 10-membered ring complexes [(OC)4M1(µ-dppe)2-M2(CO)4] have been synthesised by treating a complex of type cis-[M1(CO)4(PPh2H)2] with one of type cis-[M2(CO)4{PPh2(CHCH2)}2] in the presence of potassium t-butoxide as catalyst. The new precursor complexes cis-[M2(CO)4{PPh2(CHCH2)}2] were prepared by displacement of norbornadiene (nbd) from [M(CO)4(nbd)]. The fluxional processes in the 10-membered M1(µ-dppe)2M2 rings have been studied by variable-temperature 31P-{1H} n.m.r. spectroscopy and are characterised by a change from a second-order AA′XX′ system at 20 °C to an essentially first-order AMPX system at –90°C. The spectra have been fully interpreted and values for 2J(cis-PMP) obtained. The 31P-{1H} n.m.r. spectra of the homonuclear M(µ-dppe)2M systems change from A4 at 20 °C to AA′BB′ at –90 °C. The low-temperature (–100 °C)1H and 1H-{31P} spectra were not resolved. These binuclear complexes are remarkably inert towards disproportionation to mononuclear chelate species and to attack by HCl or halogens.
TL;DR: In this paper, it was shown that cyclofulvenes derivatives substituted at the 7 position by an exocyclic double bond can undergo ring-opening polymerisation, the catalyst system used being produced by reaction of molybdenum pentachloride with tetramethyl tin in chlorobenzene at 60-70 °C.
TL;DR: In this article, the mechanism for stereospecific dimerization of 7-t-butoxynorbornadiene catalysed by molybdenum is explained.
TL;DR: The first phosphines based on the benzo-7-phosphanorbornene system have been prepared and found to have extremely deshielded 31P nuclei as mentioned in this paper.
Abstract: The first phosphines based on the benzo-7-phosphanorbornene system have been prepared and found to have extremely deshielded 31P nuclei. The phosphine with a P-tert-butyl group gives the most downfield value (δ +152.5) ever recorded for a tertiary phosphine. The lone-pair orientation in phosphines controls the magnitude of 2J (PC) and 3J (PC), and these effects were used to determine stereochemical features of the phosphines. These compounds were formed by HSiCl3pyridine reduction of the Diels—Alder adducts of isophosphindole oxides with norbornadiene. 13C NMR was also used to confirm the assignment of these phosphine oxides.
TL;DR: The coordinating properties of the dithiaphospholane ligands R PSCH 2 CH 2 S and R PS( o -C 6 H 4 )S (R = CH3, CF3) have been studied by synthesis and spectroscopic investigations as discussed by the authors.
TL;DR: In this article, the reaction of norbornene, norbornadiene and 7-oxanorbornene with methyl 3-(chloromethyl)phenoxyacetate, (S)-1-octyn-3-ol and 8% Pd(PPh 3 ) 4 affords in one step satisfactory yields of the corresponding, first interphenylene PGH 2 analogs.
TL;DR: In this paper, the synthesis of the low molecular N,N,O,O-chelate 3.Co and its ligand 3 is optimized, which is the most active heterogenous catalysts for the valence isomerization of quadricyclane to norbornadiene.
Abstract: Starting with Z-2, 3-diamino-2-butenedinitrile as diamine component the synthesis of the low molecular N,N,O,O-chelate 3.Co and its ligand 3 is optimized. An easy synthesis of the chelate 8.Co covalently bound on macroreticular resins is presented. The chelates 8.Co are the most active heterogenous catalysts for the valence isomerization of quadricyclane to norbornadiene today.
TL;DR: In this paper, a series of electronegative substituted quadricyclanes (e.g., PEQs) were catalysed by a radicophilic attack of the metal to the corresponding norbornadiene.
TL;DR: In this article, the four-membered chelate complexes of Tellurobis(di-tert-butylphosphane) with tetracarbonyl(norbornadiene)chromium and -molybdenum (VI A) were investigated.
Abstract: Tellurobis(di-tert-butylphosphan) (1) reagiert mit Tetracarbonyl(norbornadien)chrom(0) und -molybdan(0) unter Verdrangung von Norbornadien zu den Chelatkomplexen (CO)4M[P-t-Bu2)2 Te] 2 (M Cr) und 3 (M Mo). Der entsprechende Wolframkomplex 4 (M W) wird durch Umsetzung von 1 mit dem Acetonitrilkomplexgemisch W (CO)6–n(CH3CN)n (n 2, 3) erhalten. 2 entsteht auch bei der Umsetzung von 1 mit dem Schwefelylid-Komplex (CO)4Cr[CH2S(O)(CH3)2]2. Methylenbis(di-tert-butylphosphan) (6) gibt unter gleichen Bedingungen den Vierring-Chelatkomplex (CO)4Cr[P-t-Bu2)2CH2] (8). Spektroskopische Daten (IR, MS, NMR) sowie die Kristallstrukturanalyse von 2 belegen die Funktion von 1 als sehr sperrigem zweizahnigem Phosphorliganden.
Four-membered Chelate Complexes of Tellurobis(di-tert-butylphosphane) with Tetracarbonylmetal (VI A) Acceptors
Tellurobis(di-tert-butylphosphane) (1) reacts with tetracarbonyl(norbornadiene)chromium(0) and -molybdenum(0) with formation of norbornadiene and the new chelate complexes (CO)4M-[P-t-Bu2)2)Te] 2 (M Cr) and 3 (M Mo). The corresponding tungsten complex 4 (M W) is obtained from 1 with the acetonitrile complexes W(CO)6-n(CH3CN)n (n = 2,3). The sulfur ylide complex (CO)4Cr[CH2S(O)(CH3)2]2 reacts with 1 to provide 2 and with methylenebis(di-tert-butylphosphane) (6) to the four-membered chelate complex (CO)4Cr[P-tBu2)2CH2] (8). Spectroscopic data like IR, MS and NMR and the X-ray crystal structure analysis of the chromium complex 2 provide evidence for the function of 1 as rather bulky bidentate ligand in the chelate complexes 2–4.
Patent•
17 Jan 1985
TL;DR: In this article, a clathrate compound of the compound of formula I (R is H, OH, acyloxy or alkyloxy) and cyclodextrin is irradiated with light using sun light, a high pressure mercury lamp, a low-pressure mercury lamp and a xenon lamp, etc., as light source, optionally in the presence of acetophenone, naphthoquinone, etc.
Abstract: PURPOSE:To produce the titled compound useful as an organic heat-accumulation agent free from the defects such as polymerization by light, dissipation loss, ill odor, etc., economically, by irradiating the clathrate compound of a 7-substituted norbornadiene and cyclodextrin with light. CONSTITUTION:A clathrate compound of the compound of formula I (R is H, OH, acyloxy or alkyloxy) and cyclodextrin is irradiated with light using sun light, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, etc. as light source, optionally in the presence of acetophenone, naphthoquinone, etc. to obtain the clathrate compound of the compound of formula II and cyclodextrin. Since the isomerization progresses easily even in air without producing by-products such as oxides, polymers, etc., and the obtained clathrate compound is free of the above defects, it can be used as a solar system in which the light energy is stored in the form of thermal energy by isomerization of the compound.
TL;DR: On prepare le titre en 10 etapes a partir du norbornadiene et de l'acrylonitrile as discussed by the authors, and le compose du titre in 10 andapes.
Abstract: On prepare le compose du titre en 10 etapes a partir du norbornadiene et de l'acrylonitrile