Topic
Norbornadiene
About: Norbornadiene is a research topic. Over the lifetime, 2389 publications have been published within this topic receiving 38603 citations.
Papers published on a yearly basis
Papers
More filters
TL;DR: In this paper, the crystal structure of the cycloocta-1,5-diene complex was determined using the Eyring equation, and an approximate value of 36.1 ± 0.2 kJ mol-1 for 1−3 was obtained.
Abstract: The crystal structure of [Ir(cod)(L–L)]+3[cod = cycloocta-1,5-diene, L–L = 1-(diisopropylphosphino)-1′-(diphenylphosphino)ferrocene] can be related to those of the analogous complexes with L–L = 1,1′-bis(diphenylphosphino)ferrocene (dppf)1 and 1,1′-bis(diisopropylphosphino)ferrocene (disppf), 2, all the complexes being readily synthesized from [Ir(cod)(py)2]+(py = pyridine). An optimum diphosphine bite angle of approximately 99° is maintained in all three complexes by varying the twist of the ferrocene, which decreases with increasing steric profile of the phosphine, and by distortion of the geometry at the iridium atom away from square planar towards tetrahedral. The twist about the ferrocene moiety induces chirality at the iridium atom in all three complexes and the interchange of stereoisomers can be followed by variable-temperature 1H NMR spectroscopy. Application of the Eyring equation gave approximate values of ΔG‡ for this process of 36.1 ± 0.2, 39.3 ± 0.2 and 34.3 ± 0.2 kJ mol–1 for 1–3 respectively. The ligand disoppf also induces considerable distortion away from square-planar geometry in the complex [Rh(nbd)(disoppf)][BF4]4{nbd = norbornadiene (bicyclo[2.2.1]hepta-2,5-diene)}, as found in a crystal structure determination, which may account for the unusual lability of the chelating diphosphine. This is demonstrated by its reactions with Ph2P(CH2)nPPh2(n= 1 or 2) both of which give [Rh(L–L)2]+. More surprisingly, considering its lability in [Rh(nbd)(dppf)]+, dppf also readily displaced disoppf from 4, to give [Rh(nbd)(dppf)][BF4]5. The nbd ligand in this complex is not displaced by reaction with an excess of dppf.
8 citations
TL;DR: In this article, an electronic structural study of the ground electronic states for the chemically similar bicyclic norbornadiene (NBD, C 7 H 8, X 1 A 1 ), norbornene and norbornane (NBN) molecules is provided quantum mechanically.
8 citations
TL;DR: In this article, the reaction of norbornadiene(tetracarbonyl)-chromium and -tungsten (2) with aryllithium reagents, ArLi (Ar C6H5, o-,m-,p-CH3C6H4, p-CH 3OC6H 4, p -CF3C 6H4), in ether at low temperature, and subsequent alkylation of the acylmetalate intermediates formed with Et3OBF4 in aqueous solution at 0°C
8 citations
TL;DR: In this paper, a 1:1 ratio was shown for a rare type of specific diene capture by TCTD, which is best understood in terms of normal [4+2]π cycloadditions to 8 as dienophile towards electron-deficient TCCD, followed by rapid Cope rearrangement of the SO2-bridged intermediate adducts to give the observed products.
8 citations
TL;DR: In this article, the cristallise dans P2 1 /c avec Z=4 was used for cyclooctadiene-1,5 et C 7 H 8 =norbornadiene. Affinement jusqu'a R=0,034; 0,043 et 0,047 respectivement.
Abstract: [RhC 8 H 12 (NH 3 ) 2 .C 28 H 40 O 10 ] [PF 6 ] cristallise dans P2 1 /c avec Z=4. [RhC 8 H 12 (NH 3 ) 2 .C 24 H 32 O 8 ] [PF 6 ] cristallise dans P2 1 /c avec Z=4. [RhC 7 H 8 (NH 3 ) 2 .C 24 H 32 O 8 ] [PF 6 ] cristallise dans Pbca avec Z=8. Affinement jusqu'a R=0,034; 0,043 et 0,047 respectivement. C 8 H 12 =cyclooctadiene-1,5 et C 7 H 8 =norbornadiene
8 citations