Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

作者：Crochet Aurelien; Brog Jean Pierre; Fromm Katharina M^*

来源：Crystal Growth & Design, 2016, 16(1): 189-199.

DOI：10.1021/acs.cgd.5b01084

Oxidative substitution reactions of chromium(II) chloride with lithium phenoxide in the presence of water give access to new polynudear chromium(III) aryloxide complexes and coordination polymers. While a one-dimensional coordination polymer based on chromium(II), [Cr-2(mu(3)-OPh)(2)(mu-OPh)(6)(mu-OH)(mu(3)-Li)(4)(mu(3)-Cl)(2)Li(THF)(6)](n), is first obtained by serendipity, the controlled addition of water to the initial Cr(II) complex as well as variation of the stoichiometry lead to three new discrete chromium(III) aggregates, namely, [Cr(OPh)(4)(mu-OH)Li-2(THF)(3)](2), [Cr3Li3(OPh)(9)(mu(3)-OH)(mu(3)-O)(THF)(6)], and [Cr-4(mu-OPh)(8)(mu(3)-OH)(6)(mu-OH)(2)Cl2Li6(THF)6]center dot 2THF. The use of deuterated species allowed confirmation of the oxidation based on the addition of water by detection of H-2, HD, and D-2. During these investigations, we have also identified a THF-adduct of chromium(II) chloride, [CrCl2(THF)(2)], used in the literature as a precursor in numerous syntheses, but with a hitherto unknown structure.

• 出版日期2016-1