Cobalt isomers

The molecular structure of the fra j-diferrocenyl-cobalt isomer is illustrated in Fig. 7-29 [115]. 

Coordination compounds provide many special types of constitutional isomers. Here, for example, are two cobalt isomers ... 

A key intermediate, 163, which possesses all but one chiral center of (+ )-brefeldin, has been prepared by the enantiocontrolled cycloaddition of the chiral fi,/3-unsaturated ester 162 to 154[107], Synthesis of phyllocladane skeleton 165 has been carried out by the Pd-catalyzed cycloaddition of the unsaturated diester 164 and cobalt-catalyzed cycloaddition of alkynes as key reactions[108]. Intramolecular cycloaddition to the vinylsulfone in 166 proceeds smoothly to give a mixture of the trans and cis isomers in a ratio of 2.4 1[109], Diastereocontrolled cycloaddition of the hindered vinylsulfone 167 affords a single stereoisomeric adduct, 168, which is used for the synthesis of the spirocarbocyclic ring of ginkgolide[l 10],... 

The first identified complexes of unsubstituted thiazole were described by Erlenmeyer and Schmid (461) they were obtained by dissolution in absolute alcohol of both thiazole and an anhydrous cobalt(II) salt (Table 1-62). Heating the a-CoCri 2Th complex in chloroform gives the 0 isomer, which on standirtg at room temperature reverses back to the a form. According to Hant2sch (462), these isomers correspond to a cis-trans isomerism. Several complexes of 2,2 -(183) and 4,4 -dithiazolyl (184) were also prepared and found similar to pyridyl analogs (185) (Table 1-63). Zn(II), Fe(II), Co(II), Ni(II) and Cu(II) chelates of 2.4-/>is(2-pyridyl)thiazole (186) and (2-pyridylamino)-4-(2-pyridy])thiazole (187) have been investigated. The formation constants for species MLr, and ML -" (L = 186 or 187) have been calculated from data obtained by potentiometric, spectrophotometric, and partition techniques. 

Upon treatment with suitable cobalt complexes, methylbutynol cyclizes to a 1,2,4-substituted benzene. Nickel complexes give the 1,3,5-isomer (196), sometimes accompanied by linear polymer (25) or a mixture of tetrasubstituted cyclooctatetraenes (26). 

The commercially important normal to branched aldehyde isomer ratio is critically dependent on CO partial pressure which, in propylene hydroformylation, determines the rate of interconversion of the -butyryl and isobutyryl cobalt tetracarbonyl intermediates (11). 

In contrast to triphenylphosphine-modified rhodium catalysis, a high aldehyde product isomer ratio via cobalt-catalyzed hydroformylation requires high CO partial pressures, eg, 9 MPa (1305 psi) and 110°C. Under such conditions alkyl isomerization is almost completely suppressed, and the 4.4 1 isomer ratio reflects the precursor mixture which contains principally the kinetically favored -butyryl to isobutyryl cobalt tetracarbonyl. At lower CO partial pressures, eg, 0.25 MPa (36.25 psi) and 110°C, the rate of isomerization of the -butyryl cobalt intermediate is competitive with butyryl reductive elimination to aldehyde. The product n/iso ratio of 1.6 1 obtained under these conditions reflects the equihbrium isomer ratio of the precursor butyryl cobalt tetracarbonyls (11). 

The stringency of the conditions employed in the unmodified cobalt 0x0 process leads to formation of heavy trimer esters and acetals (2). Although largely supplanted by low pressure ligand-modified rhodium-catalyzed processes, the unmodified cobalt 0x0 process is stiU employed in some instances for propylene to give a low, eg, - 3.3-3.5 1 isomer ratio product mix, and for low reactivity mixed and/or branched-olefin feedstocks, eg, propylene trimers from the polygas reaction, to produce isodecanol plasticizer alcohol. 

The earhest modification of the Oxo process (qv) employed cobalt hydrocarbonyl, HCo(CO)4, as catalyst. The reaction was carried out in the Hquid phase at 130—160°C and 10—20 MPa (1450—2900 psi) to give a ratio of n- to isobutyraldehyde of between 2 1 to 4 1. / -Butyraldehyde, the straight-chain isomer and the precursor of 2-ethylhexanol, was the more valuable product so that a high isomer ratio of n- to isobutyraldehyde was obviously advantageous. 

Physical and Chemical Properties. The (F)- and (Z)-isomers of cinnamaldehyde are both known. (F)-Cinnamaldehyde [14371-10-9] is generally produced commercially and its properties are given in Table 2. Cinnamaldehyde undergoes reactions that are typical of an a,P-unsaturated aromatic aldehyde. Slow oxidation to cinnamic acid is observed upon exposure to air. This process can be accelerated in the presence of transition-metal catalysts such as cobalt acetate (28). Under more vigorous conditions with either nitric or chromic acid, cleavage at the double bond occurs to afford benzoic acid. Epoxidation of cinnamaldehyde via a conjugate addition mechanism is observed upon treatment with a salt of /-butyl hydroperoxide (29). 

The nickel or cobalt catalyst causes isomerization of the double bond resulting in a mixture of C-19 isomers. The palladium complex catalyst produces only the 9-(10)-carboxystearic acid. The advantage of the hydrocarboxylation over the hydroformylation reaction is it produces the carboxyUc acids in a single step and obviates the oxidation of the aldehydes produced by hydroformylation. 

Quite recently, Ciampolini and coworkers have reported the synthesis of two isomeric mked oxygen-phosphorus macrocycles and the crystal structures of their cobalt complexes. Synthesis of macrocycle 27 was accomplished by condensation of 1,2-bis-(phenylphosphino)ethane dianion with 2,2 -dichlorodiethyl ether in THE. The two isomers of 27 were isolated in 1.5% and 2% yield. The synthesis is formulated in Eq. (6.17), below. 

Cobalt, dichlorobis(AvY -dimethyl-1,2-ethanediamine)-chloride hydrate isomerization, 1, 468 Cobalt, dich orobis(l,2-ethanediamine)-base hydrolysis, 1, 304 chloride anation, 1, 469 halogen exchange, 1, 468 chloride hydrate isomerization, 1, 468 isomers, 1,191 nitrate... 

Cobalt, dichloro(l, 10-diamino-4,7-dithiadecane)-configuration, 1,199 Cobalt, dichloro(triethylenetetramine)-chirality, 1,194 isomerization, 1, 467 isomers, 1,201... 

In a more recent and improved approach to cyclopropa-radicicol (228) [ 110], also outlined in Scheme 48, the synthesis was achieved via ynolide 231 which was transformed to the stable cobalt complex 232. RCM of 232 mediated by catalyst C led to cyclization product 233 as a 2 1 mixture of isomers in 57% yield. Oxidative removal of cobalt from this mixture followed by cycloaddition of the resulting cycloalkyne 234 with the cyclic diene 235 led to the benzofused macrolactone 236, which was converted to cyclopropa-radicicol (228). 

The formation of isomeric aldehydes is caused by cobalt organic intermediates, which are formed by the reaction of the olefin with the cobalt carbonyl catalyst. These cobalt organic compounds isomerize rapidly into a mixture of isomer position cobalt organic compounds. The primary cobalt organic compound, carrying a terminal fixed metal atom, is thermodynamically more stable than the isomeric internal secondary cobalt organic compounds. Due to the less steric hindrance of the terminal isomers their further reaction in the catalytic cycle is favored. Therefore in the hydroformylation of an olefin the unbranched aldehyde is the main reaction product, independent of the position of the double bond in the olefinic educt ( contrathermodynamic olefin isomerization) [49]. 

No cases of cis/trans isomerism have yet been reported among organo-cobalt(III) complexes, even among compounds not covered by this review. Complexes such as [R2Co(bipy)2] all have the cis configuration steric hindrance would be greatly increased by the coplanarity of the two bipyridyl ligands in the trans isomer 123). 

By studying the NMR spectra of the products, Jensen and co-workers were able to establish that the alkylation of (the presumed) [Co (DMG)2py] in methanol by cyclohexene oxide and by various substituted cyclohexyl bromides and tosylates occurred primarily with inversion of configuration at carbon i.e., by an 8 2 mechanism. A small amount of a second isomer, which must have been formed by another minor pathway, was observed in one case (95). Both the alkylation of [Co (DMG)2py] by asymmetric epoxides 129, 142) and the reduction of epoxides to alcohols by cobalt cyanide complexes 105, 103) show preferential formation of one isomer. In addition, the ratio of ketone to alcohol obtained in the reaction of epoxides with [Co(CN)5H] increases with pH and this has been ascribed to differing reactions with the hydride (reduction to alcohol) and Co(I) (isomerization to ketone) 103) (see also Section VII,C). 

---