Journal of the Chemical Society, Dalton Transactions p. 2299 - 2308 (1996)
Update date:2022-07-30
Topics:
Butters, Christopher
Carr, Nicholas
Deeth, Robert J.
Green, Michael
Green, Simon M.
Mahon, Mary F.
Reaction of 2-(trimethylsilyloxy)furan with the compounds cis-[Mo(NCMe)2(CO)2L][BF4] (L = η-C5H5, η-C5Me5 or η5-C9H7) afforded the η3-γ-lactonyl complexes [Mo{η3-OC(O)CHCHCH}(CO)2L]. The structure of one of these species, [Mo{η3-OC(O)CHCHCH}(CO)2(η-C5Me 5)], has been established by a single-crystal X-ray diffraction study, which confirmed that the γ-lactonyl moiety is bound to the molybdenum via three carbon atoms as an η3-allyl. Treatment of these lactonyl complexes with nucleophilic reagents (amines, methoxide) resulted in lactone ring opening and overall addition of the nucleophile to the γ-carbon of the lactone ring, rather than at the lactonyl carbonyl carbon atom as might have been expected. The product of the reaction between [Mo{η3-OC(O)CHCHCH}(CO)2(η5-C 9H7)] and PhCH2NH2 has been structurally characterised by an X-ray diffraction study as the zwitterionic, η2-alkene complex [Mo{η2-PhCH2NHCH-CH=CH(CO2H}(CO) 2(η5-C9H7)]. Similarly, [Mo{η3-OC(O)CHCHCH}(CO)2(η-C5H 5)] and methoxide anion gives, after acidification, [Mo{anti-η3-(MeO)CHCHCH(CO2H)}(CO) 2(η-C5H5)], in which the lactone ring has been cleaved to give an η3-allyl moiety ligating the metal centre. An extended Hueckel molecular orbital calculation on [Mo{η3-OC(O)CHCHCH}(CO)2(η-C5Me 5)] suggests that these reactions proceed via initial attack at the metal centre, followed by a rearrangement which effectively transfers the nucleophilic moiety to the γ-carbon of the lactone ring. Reaction of the η3-lactonyl complex [Mo{η3-OC(O)CHCHCH}(CO)2(η-C5H 5)] with HBF4·Et2O resulted in a remarkable ring-enlargement reaction, in which a co-ordinated carbon monoxide formally inserts into the lactone carbon-oxygen bond to form the crystallographically characterised complex [Mo{η3-OC(O)CHCHCHCO}(NCMe)(CO)(η-C5H 5)].
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(1996)
