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Formation of manganese enediyne complexes from manganese alkynylcarbene complexes

2003; Elsevier BV; Volume: 345; Linguagem: Inglês

10.1016/s0020-1693(02)01273-2

1873-3255

Charles P. Casey, Trevor L. Dzwiniel, Stefan Kraft, Michael A. Kozee, Douglas R. Powell,

Chemical synthesis and alkaloids

Abstract Dimerization of the alkynylcarbene complex (C5H4Me)(CO)2MnC(Tol)CCTol (10) occurred at 65 °C to give a mixture of E- and Z-enediyne complexes [(C5H4Me)(OC)2Mn]2[η2,η2-TolCC(Tol)CC(Tol)CCTol] (13). Thermolysis of alkynye complexes 10 at higher (100 °C) temperature led to the formation of manganese-free E- and Z-enediynes TolCC(Tol)CC(Tol)CCTol (14-E and 14-Z). Attempted synthesis of the tethered bis-(alkynylcarbene) complex Cp(OC)2MnC(Ph)CCCH2CH2CH2CCC(Ph)Mn(CO)2Cp led instead to the cyclic enediyne complex [Cp(OC)2Mn]2[η2,η2-PhCCC(CH2CH2CH2)CCCPh] (19), from which the metal-free enediyne 1,2-bis(phenylethynyl)cyclopentene (20) was released by thermolysis at 90 °C.