Analytical Methods in Oceanography by Gould R.F. (ed.)

By Gould R.F. (ed.)

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336 succeeded in obtaining a series of such compounds 221 by treating CpCo(C2H4)2 with a triyne as depicted in Equation (37). Cp CpCo(C2H4)2 Co R R R R ð37Þ R = H, i -Pr Cp = C5H5, C5Me5, C5H4CH3, indenyl 221 Rather good yields (72–91%) of 221 were obtained, and their relevance to the mechanism of the CpCo-catalyzed cyclization of the triyne to the angular [3]-phenylene was established by allowing 221 to rearrange thermally to 222 (see Scheme 36). Definite proofs of the structure of 221 were given more recently,337 when the same authors depicted the reaction of a closely related triyne with Cp* Co(C2H4)2, forming 223 that led to compounds 224 and 225 (Scheme 37).

The 2-cobaloxime dienyl complexes substituted in 3-position could not effect Diels–Alder reactions. To circumvent this synthetic limitation, 3-subtituted 1-cobaloximes have been synthesized (Equation (25)). 268,272 EtO EtO EtO OTs + pyr(Hdmg)2Co– EtO Co(Hdmg)2pyr ð26Þ 186 C OTs + pyr(Hdmg)2Co– C Co(Hdmg)2pyr 187 Co(OAc)2–4H2O i, DMG, Pyr, THF, Zn, Δ ii, Petasis reagent O 4 Cp2TiMe2 R L(dmg)2Co O L(dmg)2Co 179 3 CoCl2–6H2O 180 OEt L(dmg)2Co OEt OEt 181 OEt aq. 273 Another approach is to replace the dimethylglyoxime ligand set by salen ligands.

Soc. 1996, 118, 3775. ª 1996 American Chemical Society. R OC SO2 Co SO2 R = H, Me, SiMe3, CO2CH3, Me4Et, (n-allyl)5 220 Figure 50 53 54 Cobalt Organometallics Another important intermediate in the trimerization of alkynes that was never isolated is the cobaltacyclopentadiene unit to which an alkyne is 2- bound to Co. 336 succeeded in obtaining a series of such compounds 221 by treating CpCo(C2H4)2 with a triyne as depicted in Equation (37). Cp CpCo(C2H4)2 Co R R R R ð37Þ R = H, i -Pr Cp = C5H5, C5Me5, C5H4CH3, indenyl 221 Rather good yields (72–91%) of 221 were obtained, and their relevance to the mechanism of the CpCo-catalyzed cyclization of the triyne to the angular [3]-phenylene was established by allowing 221 to rearrange thermally to 222 (see Scheme 36).

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