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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)
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Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

机译：valent的二价和三价气相配位化合物：评估Cf（II）的稳定性

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摘要

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf-II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf-II(CH3SO2)(3-), prepared in the gas phase by reductive elimination of CH3SO2 from Cf-III(CH3SO2)(4-). Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of Cf-III and Sm-III, and no evidence for reduction of Cm-III. This reflects the comparative 3+/2+ reduction potentials: Cf3+ (-1.60 V) approximate to Sm3+ (-1.55 V) Cm3+ (-3.7 V). Association of O-2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. The new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf-II coordination complexes and similar chemistry of Cf and Sm.
机译：对于后来的act系元素，二价氧化态相对于三价态越来越稳定，是第一个act系元素，在中等条件下表现出二价化学性质。尽管有证据表明溶液和固体化合物中存在二价Cf，但尚无离散络合物的报道，其中Cf-II被阴离子配体配位。在此描述的是二价的Cf甲亚磺酸盐配位络合物Cf-II（CH3SO2）（3-），在气相中通过从Cf-III（CH3SO2）（4-）消除CH3SO2制备。与相应的Sm和Cm配合物的合成比较表明，Cf-III和Sm-III减少了，没有证据表明Cm-III减少了。这反映了比较的3 + / 2 +还原电位：Cf3 +（-1.60 V）近似于Sm3 +（-1.55 V） Cm3 +（-3.7 V）。 O-2与二价络合物的缔合归因于超氧化物的形成以及三价氧化态的恢复。 now的新型气相化学，现在已是通过这种方式研究的最重的元素，为Cf-II配位络合物以及Cf和Sm的类似化学提供了证据。

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