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The reaction of the syn -bimetallic bis(pentalene)dititanium complex Ti 2 (μ:η 5 ,η 5 -Pn † ) 2 (Pn † = C 8 H 4 (1,4-Si i Pr 3 ) 2 ) 1 with carbon suboxide (O[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]O, C 3 O 2 ) results in trimerisation of the latter and formation of the structurally characterised complex [{Ti 2 (μ:η 5 ,η 5 -Pn † ) 2 }{μ-C 9 O 6 }]. The trimeric bridging C 9 O 6 unit in the latter contains a 4-pyrone core, a key feature of both the hexamer and octamer of carbon suboxide which are formed in the body from trace amounts of C 3 O 2 and are, for example, potent inhibitors of Na + /K + -ATP-ase. The mechanism of this reaction has been studied in detail by DFT computational studies, which also suggest that the reaction proceeds via the initial formation of a mono-adduct of 1 with C 3 O 2 . Indeed, the carefully controlled reaction of 1 with C 3 O 2 affords [Ti 2 (μ:η 5 ,η 5 -Pn † ) 2 (η 2 -C 3 O 2 )], as the first structurally authenticated complex of carbon suboxide.

Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system