tert-Butoxycopper-carbonyl and tert-butoxycopper-tert-butyl isocyanide. New and sublimable copper-carbonyl and isocyanide complexes
tert-Butoxycopper-carbonyl and tert-butoxycopper-tert-butyl isocyanide. New and sublimable copper-carbonyl and isocyanide complexes
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DOI：
10.1021/ja00825a036
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发表时间：
1974-09
影响因子：
15
通讯作者：
T. Tsuda;Haruo Habu;Sadashige Horiguchi;T. Saegusa
中科院分区：
文献类型：
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作者：
T. Tsuda;Haruo Habu;Sadashige Horiguchi;T. Saegusa
第5931章金属的属性6游离Z-BuNC的y（C== N）显著降低（p（C= N）= 2138 cm-1）。据我们所知，这是第一个异氰化铜络合物表现出如此显著的y（C= N）还原的例子。例如，Z-BuNC· CuCl和Z-BuNC CuO Ac 7的i/（CsN）分别为2189和2169 cm-1。A5-C5 H5 Cu· CN-Z-Bu的值为2170 cm-1.8因此，2中的Z-BuNC配体借助ZerZ-丁氧基配体的贡献，成为铜的良好受体。一价铜-烷氧基键对插入一氧化碳和异氰化物的惰性与二价铜-烷氧基键的高反应性形成鲜明对比。9用一氧化碳和Z-BuNC容易地还原（z-BuO）2Cu，并且通过升华获得1和2（等式1和2）。10 co（t-BuO）2Cu-> i-BuOCu CO+ t-BuOCO-i-Bu（60%）苯，90
5931 upon thenature of metal. 6 The considerablelowering of y (C== N) in 2 is significant (p (C= N) of free Z-BuNC, 2138 cm-1). To our knowledge, this is the first ex-ample of a copper-isocyanide complex exhibiting such a remarkable reduction of y (C= N). For example, i/(CsN) of Z-BuNC· CuCl and Z-BuNC CuO Ac7 are 2189 and 2169 cm-1, respectively. A5-C5H5Cu· CN-Z-Bu has a value of 2170 cm-1.8 Thus, Z-BuNC ligand in 2 functions as a good-acceptor for copper by the aid of-donation from ZerZ-butoxy ligand. The inertness of the univalent copper-alkoxy bond toward insertions of carbon monoxide and isocyanide sharply contrasts with a high reactivity of the divalent copper-alkoxy bond. 9 Reduction of (z-BuO) 2Cu with carbon monoxide and Z-BuNC took place readily, and 1 and 2 were obtained by sublimation (eq 1 and 2). 10 co (/-BuO) 2Cu-> i-BuOCu CO+ r-BuOCO-i-Bu (60%) benzene, 90