Tsoureas Nikolaos, Green Jennifer C, Cloke F Geoffrey N, Puschmann Horst, Roe S Mark, Tizzard Graham
School of Life Sciences , Department of Chemistry , University of Sussex , Falmer , Brighton , BN1 9QJ , UK . Email:
Department of Chemistry , University of Oxford , Inorganic Chemistry Laboratory , South Parks Road , Oxford OX1 3QR , UK.
Chem Sci. 2018 May 8;9(22):5008-5014. doi: 10.1039/c8sc01127c. eCollection 2018 Jun 14.
The reaction of the -bimetallic bis(pentalene)dititanium complex Ti(μ:η,η-Pn) (Pn = CH(1,4-SiPr)) 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, CO) results in trimerisation of the latter and formation of the structurally characterised complex [{Ti(μ:η,η-Pn)}{μ-CO}]. The trimeric bridging CO 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 CO 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 the initial formation of a mono-adduct of with CO. Indeed, the carefully controlled reaction of with CO affords [Ti(μ:η,η-Pn) (η-CO)], as the first structurally authenticated complex of carbon suboxide.
双金属双（戊搭烯）二钛配合物Ti(μ:η,η-Pn)（Pn = CH(1,4-SiPr)）与三氧化二碳（O[双键，长度为m破折号]C[双键，长度为m破折号]C[双键，长度为m破折号]C[双键，长度为m破折号]O，即CO）反应，导致后者三聚，并形成结构已表征的配合物[{Ti(μ:η,η-Pn)}{μ-CO}]。后者中的三聚桥连CO单元包含一个4-吡喃酮核心，这是三氧化二碳六聚体和八聚体的一个关键特征，三氧化二碳六聚体和八聚体在体内由痕量的CO形成，例如，是Na/K-ATP酶的有效抑制剂。通过密度泛函理论（DFT）计算研究对该反应的机理进行了详细研究，计算研究还表明该反应是通过 与CO最初形成单加合物进行的。实际上， 与CO经过精心控制的反应得到了[Ti(μ:η,η-Pn)(η-CO)]，这是首个结构已确认的三氧化二碳配合物。
