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Norbornadiene
About: Norbornadiene is a research topic. Over the lifetime, 2389 publications have been published within this topic receiving 38603 citations.
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TL;DR: For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.
Abstract: The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.
26 citations
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TL;DR: The complex chemical behavior of 2-phosphaindolizines towards metal carbonyl compounds was studied in this paper, where the influence of substituents and metals on the 31P and 13C complexation chemical shifts and coupling constants was discussed.
Abstract: The complex chemical behaviour of 2-phosphaindolizines 1 (1,3-azaphospholo[1,5-a]pyridines) towards metal carbonyl compounds was studied. (η1-2-Phosphaindolizine)M(CO)5 complexes 2–4 (M = Cr, Mo, W) were formed from 1 and [(THF)M(CO)5], the cis-L2Cr(CO)4 complex 5f from 1f and tetracarbonyl(norbornadiene) chromium(0). The reaction of 2-phosphaindolizines 1e, 1f, or 1g with tricarbonyl(cycloheptatriene)molybdenum(0) or tricarbonyl(mesitylene)tungsten(0) yielded σ-complexes of the types L2M(CO)4or L3M(CO)3 rather than isolable π-complexes. In one case a strong upfield signal (δ31P = 6.1) was observed with a coordination shift of Δδ = –161.7, which is typical for π-coordination. Prolonged reaction or work-up led, however, to dismutation yielding 1g and the fac-L3Mo(CO)3 complex 6g. X-ray structure analysis of 2a indicates an increased 10π-delocalization compared with 1a and a changed conformation of the acyl substituent. The influence of substituents and metals on the 31P and 13C complexation chemical shifts and coupling constants is discussed.
26 citations
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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...
26 citations
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TL;DR: In this article, it was found that carbenes undergo extensive addition to the endo-face of norbornadiene, yeilding the cheletropic adduct, 4.4-difluorotetracyclo[3.3.0.02,8.03,6]-octane.
Abstract: It has been found that difluorocarbene undergoes extensive addition to the endo-face of norbornadiene, yeilding the cheletropic adduct, 4.4-difluorotetracyclo[3.3.0.02,8.03,6]-octane. Similar behaviour has been observed for fluorochlorocarbene. Possible mechanisms to rationalize this novel behaviour of carbenes are discussed.
26 citations