Formation, expansion, and interconversion of metallarings in a sulfur-bridged Au(I) Co(III) coordination system.

Formation, expansion, and interconversion of metallarings in a sulfur-bridged Au(I) Co(III) coordination system.
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硫桥 Au(I) Co(III) 配位体系中金属化合物的形成、膨胀和相互转化。

DOI:
10.1002/anie.201309986
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发表时间:
2014
期刊:
影响因子:
--
通讯作者:
T. Konno
T. Konno
中科院分区:
--
文献类型:
--
作者:
Katsuya Oji;A. Igashira;N. Yoshinari;T. Konno

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由新制备的[Co(D-nmp)2](-)(1)(-)衍生的新型Au(I) Co(III)配位体系报道了D-nmp= n -甲基- d -青霉胺酸)和金(I)前体Au(I)。配合物1(-)作为供硫金属配体,与金(I)前体反应生成具有八元Au(I) 2 Co(III) 2金属化的[Au2 Co2 (D-nmp)4](2)。用[Au2 (dppe)2](2+) (dppe=1,2-双(二苯基膦)乙烷)处理2生成[Au4 Co2 (dppe)2 (D-nmp)4](2+)(3(2+)),由18元Au(I) 4 Co(III) 2金属化组成,可容纳四面体阴离子(BF4 (-), ClO4 (-), ReO4(-))。在溶液中,3(2+)的金属化结构很容易与九元Au(I) 2 Co(III)的金属化结构[Au2 Co(dppe)(D-nmp)2](+)(4(+))相互转换;这一过程取决于外部因素,如溶剂、浓度和反阴离子的性质。这些结果揭示了Au - S键和Au - P键的不稳定性,这是金属化膨胀和收缩所必需的。
A novel Au(I) Co(III) coordination system that is derived from the newly prepared [Co(D-nmp)2 ](-) (1(-) ; D-nmp=N-methyl-D-penicillaminate) and a gold(I) precursor Au(I) is reported. Complex 1(-) acts as a sulfur-donating metallaligand and reacts with the gold(I) precursor to give [Au2 Co2 (D-nmp)4 ] (2), which has an eight-membered Au(I) 2 Co(III) 2 metallaring. Treatment of 2 with [Au2 (dppe)2 ](2+) (dppe=1,2-bis(diphenylphosphino)ethane) leads to the formation of [Au4 Co2 (dppe)2 (D-nmp)4 ](2+) (3(2+) ), which consists of an 18-membered Au(I) 4 Co(III) 2 metallaring that accommodates a tetrahedral anion (BF4 (-) , ClO4 (-) , ReO4 (-) ). In solution, the metallaring structure of 3(2+) is readily interconvertible with the nine-membered Au(I) 2 Co(III) metallaring structure of [Au2 Co(dppe)(D-nmp)2 ](+) (4(+) ); this process depends on external factors, such as solvent, concentration, and nature of the counteranion. These results reveal the lability of the AuS and AuP bonds, which is essential for metallaring expansion and contraction.
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