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• W1971014901 startingPage "1539" @default.
• W1971014901 abstract "The cyclohexadienyl complexes [Mn(η5-C6H6R1)(CO)3]1(R1=exo-H, Me or C6H4Me-4) react with LiR2(R2= Me or Ph) to give acylmetalates [Li(OEt2)][Mn(η5-C6H6R1)(CO)2{C(O)R2}]2. Complex 2(R1= Me, R2= Ph) has been characterised by an X-ray crystallography study: orthorhombic, space group P212121, a= 9.113(2), b= 14.491(8), c= 32.803(9)Å, R= 0.064 for 1458 independent reflections. Protonation of 2 with HBF4·Et2O induces an aryl- or alkyl-group transfer to the endo face of the cyclohexadienyl ring yielding the new agostic cyclohexenyl complexes [Mn(η3:CHC6H7R1R2)(CO)3]3. The cyclohexenyl ligands can be decomplexed from the metal via treatment of 3 with 1,2-bis-(diphenylphosphino)ethane (dppe) in tetrahydrofuran to afford mixtures of substituted cyclohexa-1,3-dienes and [MnH(CO)3(dppe)]. The acylmetalates 2 react with [NO][BF4] at –78 °C to give [Mn(η5-C6H6R1)(CO)(NO){C(O)R2}] which decompose at room temperature to form the trans-disubstituted acylcyclohexadienes C6H6R1[C(O)R2]. Reaction of 2 with electrophiles SiMe3Cl, [Me3O][BF4] or [Et3O][BF4] results in O alkylation and formation of stable carbene complexes [Mn(η5-C6H6R1)(CO)2{C(OE)R2}](E = SiMe3, Me or Et)." @default.
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• W1971014901 date "1992-01-01" @default.
• W1971014901 modified "2023-10-11" @default.
• W1971014901 title "Synthesis and reactions of acyl(cyclohexadienyl)manganates" @default.
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• W1971014901 doi "https://doi.org/10.1039/dt9920001539" @default.
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