Norbomadiene complexes

Nonsteroidal antiinflammatory drugs, interaction with lithium, 36 66 No-phonon transition, 35 324 Norbomadiene complexes with cobalt, 12 286 with copper, 12 328, 330, 331 with gold, 12 348, 349 with group VIB metals, 12 231 with group VnB metals, 12 241 with iron, 12 265 with palladium, 12 314 with platinum, 12 319 with rhodium, 12 300-302 with ruthenium, 12 278, 279 with silver, 12 340-342, 344, 346 Norbomylsiloxane, 42 226, 228 Notch receptor proteins, 46 473, 475 h (N)" oxime complexes, osmium, 37 260 h (N,0) oxime complexes, osmium, 37 260 (NPr ljiFeCfrdto),], magnetization versus temperature, 43 230... 

Additional regio- and stereo-chemical information was obtained from palladium-ene reactions of strained alkenes. An instructive example is the reaction of stoichiometric amounts of the allylpalladium species (52) which undergo rapid, reversible formation of the cr-allylpalladium-norbomadiene complexes (53) to give at 37 °C the cis insertion products (54) (Scheme 12). Carbon-carbon bond formation (at the least substituted allyl terminal) and palladium transfer from the same (exo) face of norbomadiene were ascribed" to a o-allypalladium alkene insertion. 

The cyclopropylmethyl subunit can be incorporated into a polycyclic system. Thus, endo-3-metalated nortricyclenes 6 were obtained from norbomadiene complexes 4 of platinum or palladium via exo addition of nucleophiles and intramoleeular alkene insertion converting the homoallylic subunit to a cyclopropylmethylmetal complex (see also Seetion 5.2.6.2.)... 

Under carbonylation conditions, both the homoallylic adduct and the nortricyclene system derived from norbomadiene complexed with methanol to give methyl exo-5-methoxytri-cyclo[2.2.1.0 ]heptane-e r/o-3-carboxylate (18). ... 

A mixture of the norbomadiene complex (5.0 g, 18.5 mmol) and dry benzene (135mL) was placed in a 500-mL, glass-lined autoclave. The autoclave was sealed and pressurized with CO (33 atm), and the contents of the autoclave were stirred at 90 °C for 83 h. The solid residue was removed by filtration. The filtrate was combined with MeOH (50 mL) and the resulting mixture was heated to reflux temperature for 1 h. The solution was concentrated and the residue extracted with pentane. After removal of pentane by distillation 1.3 g of residual liquid was obtained. The major component of this crude material (> 90%) was purified by preparative GC (20 ft x 0.375 in., 15% SE-30/Chromsorb W column). 

Cycloheptadiene interacts slowly with Rh(CO)2(acac), simultaneously undergoing isomerization, to give the norbomadiene complex (C7Hg)Rh(acac) (74). 

The synthesis and X-ray crystal structures of two iron norbomadiene complexes of the type [Fe(CO)2(T -NBD)(L)] (L = CNMe, PPh3) has been reported206. When L = NCMe, the coordination about the iron was found to be essentially trigonal bipyramidal with the axial positions occupied by CNMe and one C=C bond. When L = PPh3, the coordination geometry was found to be close to square pyramidal, with an axial CO ligand. The relevance of these stractures to rotation of the diene in [Fe(CO)3(Ti -diene)] complexes was discussed. 

The high catalytic activity and regioselectivity displayed by rhodium norbomadiene complexes of the type rac-[Rh2( n -NBD)2(PP)P , (18), and meso-[Rh2(Tl -NBD)2(PP)] (PP = Et2PCH2CH2P(Ph)CH2P(Ph)CH2CH2PEt2) in alkene hydroformylation reactions has been... 

It has been established34 that the reaction of the nortricydic compound, A, with a silver salt in MeCN results in the formation of a solvento-complex containing a coordinated acetonitrile ligand. In acetone solution, halide abstraction is followed by isomerization of the ligand, ring-dosure, and the formation of the norbomadiene complex, B, Figure 6.2. 

The crystal structure 1 of the norbomadiene complex (C7H[Pg.26]

C=C distances in the cyclo-octatetraene do not appear to be lengthened [78]. The norbomadiene complex CTHt(AgN03)2 is similar to the cyclo-octatetraene complex 1.10, in that it consists of Ag-NOs chains link by the olefin [78u]. In refluxing solutions of silver salts in cyclo-octatetraene the < clo-octatetraene may dimerize forming a number of isomeric olefins... 

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