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

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

The reaction of the syn-bimetallic bis(pentalene)dititanium complex Ti2(μ:η55-Pn)2 (Pn = C8H4(1,4-SiiPr3)2) 1 with carbon suboxide (OCCCO, C3O2) results in trimerisation of the latter and formation of the structurally characterised complex [{Ti2(μ:η55-Pn)2}{μ-C9O6}]. The trimeric bridging C9O6 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 C3O2 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 C3O2. Indeed, the carefully controlled reaction of 1 with C3O2 affords [Ti2(μ:η55-Pn)22-C3O2)], as the first structurally authenticated complex of carbon suboxide.

2041-6520
5008-5014
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
Green, Jennifer C.
6215aa99-d154-451b-a6ce-cd9b98ea6738
Cloke, F. Geoffrey N.
9582efcd-a534-44a2-9b0c-d90ad7428aff
Puschmann, Horst
f3f15506-e694-4722-8112-c1175bfc12f0
Roe, S. Mark
e79cf104-6593-43e1-b5b0-2991127f6bad
Tizzard, Graham
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
Green, Jennifer C.
6215aa99-d154-451b-a6ce-cd9b98ea6738
Cloke, F. Geoffrey N.
9582efcd-a534-44a2-9b0c-d90ad7428aff
Puschmann, Horst
f3f15506-e694-4722-8112-c1175bfc12f0
Roe, S. Mark
e79cf104-6593-43e1-b5b0-2991127f6bad
Tizzard, Graham
8474c0fa-40df-43a6-a662-7f3c4722dbf2

Tsoureas, Nikolaos, Green, Jennifer C., Cloke, F. Geoffrey N., Puschmann, Horst, Roe, S. Mark and Tizzard, Graham (2018) Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system. Chemical Science, 9 (22), 5008-5014. (doi:10.1039/c8sc01127c).

Record type: Article

Abstract

The reaction of the syn-bimetallic bis(pentalene)dititanium complex Ti2(μ:η55-Pn)2 (Pn = C8H4(1,4-SiiPr3)2) 1 with carbon suboxide (OCCCO, C3O2) results in trimerisation of the latter and formation of the structurally characterised complex [{Ti2(μ:η55-Pn)2}{μ-C9O6}]. The trimeric bridging C9O6 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 C3O2 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 C3O2. Indeed, the carefully controlled reaction of 1 with C3O2 affords [Ti2(μ:η55-Pn)22-C3O2)], as the first structurally authenticated complex of carbon suboxide.

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c8sc01127c
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Accepted/In Press date: 5 May 2018
e-pub ahead of print date: 8 May 2018

Identifiers

Local EPrints ID: 421674
URI: http://eprints.soton.ac.uk/id/eprint/421674
ISSN: 2041-6520
PURE UUID: 0c5ec75b-3c5c-4bd9-8c72-336ec05e7668
ORCID for Graham Tizzard: ORCID iD orcid.org/0000-0002-1577-5779

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Date deposited: 21 Jun 2018 16:30
Last modified: 07 Oct 2020 01:46

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