Evidence of zinc superoxide formation in the gas phase: Comparisons in behaviour between ligated Zn(I/II) and Cu(I/II) with regard to the attachment of O_2 or H_2O

Cox H.; Norris C.; Wu G.; Guan J.; Hessey S.; Stace A.J.

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Evidence of zinc superoxide formation in the gas phase: Comparisons in behaviour between ligated Zn(I/II) and Cu(I/II) with regard to the attachment of O_2 or H_2O

机译：气相中形成过氧化锌的证据：连接的Zn（I / II）和Cu（I / II）在O_2或H_2O附着方面的行为比较

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Singly and doubly charged atomic ions of zinc and copper have been complexed with pyridine and held in an ion trap. Complexes involving Zn(ii) and Cu(i) (3d~(10)) display a strong tendency to bind with H2O, whilst the Zn(i) (3d~(10)4s~1) complexes exhibit a strong preference for the attachment of O_2. DFT calculations show that this latter result can be interpreted as internal oxidation leading to the formation of superoxide complexes, [Zn(ii)O_2~-](pyridine)_ n, in the gas phase. The calculations also show that the oxidation of Zn(i) to form Zn(ii)O_2~- is promoted by a mixing of the occupied 4s and vacant 4p orbitals on the metal cation, and that this process is facilitated by the presence of the pyridine ligands.

机译：锌和铜的单双电荷原子离子已与吡啶络合并保持在离子阱中。涉及Zn（ii）和Cu（i）（3d〜（10））的配合物表现出很强的与H2O结合的趋势，而Zn（i）（3d〜（10）4s〜1）配合物表现出对H2O的强烈偏好。 O_2的附件。 DFT计算表明，后者的结果可以解释为内部氧化导致气相中形成[Zn（ii）O_2〜-] [吡啶] _n超氧化物配合物。计算结果还表明，金属离子上占据的4s和空位4p轨道的混合促进了Zn（i）的氧化形成Zn（ii）O_2〜-，并且该过程的存在也促进了该过程。吡啶配体。

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《Dalton transactions: An international journal of inorganic chemistry》 |2011年第42期|共11页
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Cox H.; Norris C.; Wu G.; Guan J.; Hessey S.; Stace A.J.;
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Evidence of zinc superoxide formation in the gas phase: Comparisons in behaviour between ligated Zn(I/II) and Cu(I/II) with regard to the attachment of O_2 or H_2O

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