Norbornadiene complexes with cobalt

The intermolecular Pauson-Khand reaction of the resulting S/P-cobalt complexes with norbornadiene was studied under thermal and A -oxide activation conditions. Thus, heating the diastereomerically pure complex (R = Ph, R = Cy) with ten equivalents of norbornadiene at 50 °C in toluene afforded the corresponding exo-cyclopentenone in a quantitative yield and with an enantio-selectivity of 99% ee. Under similar conditions, the analogous trimethylsilyl complex (R = TMS, R = Cy) afforded the expected product in a high yield but with a lower enantioselectivity of 57% ee. In order to increase this enantio-selectivity, these authors performed this reaction at room temperature in dichloromethane as the solvent and in the presence of NMO, which allowed an enantioselectivity of 97% ee to be reached. These authors assumed that the thermal activation promoted the isomerisation of the S/P ligand leading to a nonstereoselective process. 

Of the cyclic olefins, norbornadiene replaces two CO groups from one Co to yield a labile complex 159, 160, 235), cyclooctatetraene replaces the axial CO ligands from all three cobalt atoms 53) and is itself replaced by other Lewis bases 330), and cyclopentadiene forms the unusual complex [95] with Co3(CO)gCMe 159,160). A few catalytic reactions were observed with methinyltricobalt enneacarbonyls including the dimerization of norbornadiene 160, 235) and the polymerization of functional olefins 312) with different Co3(CO)9CX. 

A tetracobalt anionic complex, viz. [In Co(CO)4 4] (27) (37,37a), has been briefly described together with the thallium analogue (28) (37a), both formed by addition of [Co(CO)4] to either 25 or 26. No structural details have been reported although the indium and thallium centers are presumably tetrahe-drally coordinated by the four cobalt atoms. Mention is also made (37a) of the facile heterolytic bond dissociation (In—Co or Tl—Co) observed in polar solvents. Little has been reported about the reactivity of these complexes, although a discussion on the use of 25 as a catalyst in the dimerization of norbornadiene has appeared (58). 

They noted that in dimethoxyethane or in iso-octane (path a), the major product was dicarbonylcyclopentadienylcobalt (2) which must arise as a result of a retro Diels-Alder reaction of the norbornadiene (which would lead to the formation of acetylene and cyclopentadiene). When the solvent was changed to an aromatic hydrocarbon such as benzene or toluene (path b), the major cobalt-containing product was shown to be a complex derived from Co4(CO)i2, with three CO ligands on an apical cobalt being replaced by a molecule of the aromatic solvent (3). The group noted that they were also obtaining hydrocarbon and ketonic products derived from norbornadiene, acetylene and carbon monoxide .1,2... 

Protonation of (norbornadiene)cobalt complex 43 induces C-C bond cleavage of the norbornenyl ring to form cationic complex 44 [63,64]. Re-protonation of the reduced complex 45 induces a second cleavage of a non-strained cyclopen-tene ring to give an open r)5-pentadienyl complex 46. It is postulated that a three-center interaction of the highly electrophilic metal center with the a-electrons of the adjacent C-C bond is involved. 

Homo-Diels-Alder reactions occur between norbornadiene and norbornene or unactivated alkynes giving 14 and 15a-e , respectively, by using as catalyst the cobalt complex obtained by reducing tris(acetylacetonato)cobalt with diethylaluminum chloride in the presence of bis(l, 2-diphenylphosphino)ethane." ... 

The use of transition metal complexes as catalysts allows 1,4-cycloadditions to be involved as the major pathway in several cases when conjugated dienes are reacted with norbornadiene. No normal homo-Diels-Alder reaction was observed by reaction of the latter with buta-1,3-diene in the presence of an iron complex catalyst, the main product obtained was such a 1,4-adduct 2f the same adduct 2 was obtained in good yield and selectivity when a catalyst formed from cobalt(II) chloride, diethylaluminum chloride and bis(l,2-diphenylphos-phinojethane was used. ... 

Similar reactions of norbornadiene with substituted buta-1,3-dienes in the presence of cobalt catalysts lead to the corresponding 1,4-adducts in 92-96% yield.In the presence of chiral phosphane ligands, this reaction has been brought about with up to 79% enantiomeric excess. The head-to-head dimer of norbornadiene, 1,2,4 5,6,8-dimethano-5-indacene (3, Binor-S ) was formed in quantitative yield on dimerizing norbornadiene with catalysts such as co-balt(II) bromide/triphenylphosphane, cobalt(ll) iodide/triphenylphosphane, or (triphenylphos-phanejrhodium chloride, in the presence of boron trifluoride-diethyl ether complex. ... 

The most efficient catalysts for the homo Diels-Alder reactions of norbornadiene were found to be cobalt and nickel complexes. The general mechanistic pathway that has been proposed for these reactions has been depicted in equation 161. According to this mechanism, co-ordination of norbornadiene and the olefin or acetylene to the metal center gives 557, which is in equihbrium with metallocyclopentane complex 558. Then, insertion of the olefin or acetylene in the metal-carbon bond takes place to form 559. Reductive elimination finally liberates the deltacyclane species. 

Norbornene or norbornadiene-type substrates with nickel, ruthenium or cobalt catalysts undergo stereoselective dimerization or codimerizations with other substrates. Numerous examples have been reported15. Stoichiometric use of an iridium complex in the cyclodimerization of norbornadiene results in an isolable c.vo-rrans-c.ro-metallacyclopentane 7, formed from two norbornadiene units18. Upon heating in the presence of triphenylphosphanc, the exo-trans-e.YO-dimer 8 is liberated from complex 7. 

The use of both LIU and HIU has been shown to increase the efficiency of the P-K reaction, which involves the formation of cyclopentenone from the annulation of a cobalt alkynyl carbonyl complex and an alkene. The use of low-power ultrasound, as for example, from a cleaning bath, although capable of producing intramolecular P-K reactions, generated relatively low cyclization yields. The motivation for the use of high intensity came from its ability, as previously described, to effectively decarbonylate metal carbonyl and substituted metal carbonyl complexes. Indeed, HIU produced by a classic horn-type sonicator has been shown to be capable of facile annulation of norbornene and norbornadiene in under 10 min in the presence of a trimethylamine or trimethylamine N-oxidc dihydrate (TMANO) promoter, with the latter promoter producing cleaner product mixtures. This methodology also proved effective in the enhancement of the P-K reaction with less strained alkenes such as 2,5-dihydrofuran and cyclopentene, as well as the less reactive alkenes -fluorostyrene and cycloheptene. The mechanism has been postulated to involve decarbo-nylation of the cobalt carbonyl alkyne, followed by coordination by the amine to the vacant coordination sites on the cobalt. 

A different skeletal rearrangement reaction of norbornadiene takes place on cobalt (Scheme 7.7) [9]. Protonation of the (norbornadiene)cobalt complex 19 induced C-C bond cleavage of the norbornenyl ring to form the cationic aUyl-cobalt complex 20. Reduction with LiBHEtj formed the neutral diene complex 21, which undergoes further C-C bond cleavage upon treatment with acid to give the T -pentadienyl complex 22. 

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