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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Reactions of Complex Ligands. Part 107 [1] Densely Substituted Hydroquinoid Phenanthrene and Triphenylene Cr(CO)(3) Complexes: Chromium-Templated Synthesis and Molecular Structure
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Reactions of Complex Ligands. Part 107 [1] Densely Substituted Hydroquinoid Phenanthrene and Triphenylene Cr(CO)(3) Complexes: Chromium-Templated Synthesis and Molecular Structure

机译：复杂配体的反应。第107部分[1]重取代的对苯二酚菲和三亚苯基Cr（CO）（3）配合物：铬模板合成和分子结构

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摘要

Densely Substituted hydroquinoid phenanthrene (1018), acephenanthrene (19), and triphenylene chromium tricarbonyl complexes (20-22) have been prepared via benzannulation of naphthalenyl (1-7), acenaphthenyl (8) and phenanthrenyl carbene complexes (9), respectively. The naphthalenyl, acenaphthenyl and phenanthrenyl carbene complexes 1-9 were obtained in 52-88% yield starting from commercially available bromoarenes by dehalolithiation, addition of hexacarbonyl chromium to the lithioarene and O-alkylation of the resulting acyl chromates with trimethyloxonium tetrafluoroborate (Fischer route). The benzannulation of the aryl carbene complexes (either with 3-hexyne / (t-butyl)dimethylsilyl chloride or with (t-butyl)dimethylsilylethyne) allowed the regio-specific synthesis of the oligocyclic hydroquinoid arene tricarbonyl chromium complexes 10-22 in 44-94% yield thus providing a two-step synthesis with overall yields of 18 - 80%. Under the kinetic reaction conditions used the metal atom is exclusively coordinated to the persubstituted terminal hydroquinoid ring. The molecular structures of phenanthrene complexes 10, 12-14, and 16, acephenanthrene complex 19, and triphenylene complexes 20 and 21 in the solid state have been determined by X-ray crystallography The carbonyl ligands either adopt an eclipsed (10, 12, 14, 16 19 20) or staggered (13, 21) exo-conformation pointing away from the center of the phenanthrene, acephenanthrene and triphenylene ligands, respectively. The coordination of the metal atom to the hydroquinoid ring is unsymmetric with the largest metal-carbon distances found between the chromium atom and one bridgehead carbon and the ring carbon atom bearing the bulky (t-butyl)dimethylsilyloxy (TBDMSO) substituent.
机译：分别通过萘（1-7），（8）和菲卡宾（9）的苯并环合反应制备了重取代的对苯二酚菲（1018），对菲（19）和三苯铬三羰基铬配合物（20-22）。萘基，基和菲基卡宾配合物1-9以52-88％的产率从市售的溴芳烃开始进行脱卤代反应，向六硫代芳烃中添加六羰基铬，然后将所得的铬酸铬与四氟硼酸三甲基氧鎓进行O-烷基化（费舍尔路线） 。芳基卡宾配合物（与3-己炔/（叔丁基）二甲基甲硅烷基氯或与（叔丁基）二甲基甲硅烷基乙炔）的苯并环合可以在44-产率为94％，因此提供了两步合成，总产率为18-80％。在所用的动力学反应条件下，金属原子仅与全取代的末端氢醌环配位。已通过X射线晶体学测定了固态的菲配合物10、12-14和16，对菲配合物19和三亚苯基配合物20和21的分子结构。羰基配体要么偏色（10、12、14 ，16 19 20）或交错（13，21）外构象分别背向菲，对菲和三亚苯基配体的中心。金属原子与氢醌环的配位是不对称的，在铬原子与一个桥头碳和带有大体积（叔丁基）二甲基甲硅烷氧基（TBDMSO）取代基的环碳原子之间发现最大的金属碳距离。

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