Transition metal-stabilized arenium cations: Protonation of arenes dihapto-coordinated to π-basic metal fragments
Transition metal-stabilized arenium cations: Protonation of arenes dihapto-coordinated to π-basic metal fragments
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DOI：
10.1021/ja039824h
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发表时间：
2004-06-02
影响因子：
15
通讯作者：
Harman, WD
中科院分区：
文献类型：
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作者：
Keane, JM;Chordia, MD;Harman, WD
合成了一系列金属配合物，其中芳烃与具有通式{TpM（π-酸）（L）}的π-碱性金属片段双半配位，其中Tp =三（吡唑基）硼酸盐，M =钼、钼或钨，π-酸= CO或NO+，并且L = 1-甲基咪唑、1-丁基咪唑、吡啶或三甲基膦。芳烃配合物被证明是显着更基本的比类似的pentaammineosmium（II）芳烃配合物，并质子化的温和的酸，得到非常稳定的eta（2）和eta（3）arenium阳离子配合物。[TpRe（CO）（Melm）（5，6-eta（2）-2 H-anisolium）]（OTf）的晶体结构证实了anisolium配体的eta（2）配位，但表明金属与anisolium的C1之间存在弱的长程相互作用。
A series of metal complexes was synthesized in which arenes were dihapto-coordinated to pi-basic metal fragments having the general form {TpM(pi-acid)(L)}, where Tp = hydridotris (pyrazolyl)borate, M = rhenium, molybdenum, or tungsten, pi-acid = CO or NO+, and L = 1-methylimidazole, 1-butylimidazole, pyridine, or trimethylphosphine. The arene complexes were shown to be significantly more basic than the analogous pentaammineosmium(II) arene complexes and were protonated by moderate acids to give remarkably stable eta(2) and eta(3) arenium cation complexes. A crystal structure of [TpRe(CO)(Melm)(5,6-eta(2)-2H-anisolium)](OTf) confirmed the eta(2) coordination of the anisolium ligand, but suggests a weak long-range interaction between the metal and C1 of the anisolium.