Synthesis of a room-temperature-stable dimeric copper(I) hydride.
Synthesis of a room-temperature-stable dimeric copper(I) hydride.
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DOI：
10.1002/asia.201000576
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发表时间：
2011-02-01
影响因子：
4.1
通讯作者：
Bertrand, Guy
中科院分区：
文献类型：
--
作者：
Frey, Guido D.;Donnadieu, Bruno;Soleilhavoup, Michele;Bertrand, Guy
早在1844年就发现了[1]，铜（I）氢化物配合物引起了相当大的兴趣。与氢硅烷组合作为氢化物源，它们促进酮和醛的氢化硅烷化，并且它们是许多羰基衍生物（包括不饱和酮、醛和酯）的区域选择性共辄还原中的有效催化剂。[2]最广泛研究的氢化铜无疑是六聚体[（Ph3P）CuH] 6，首先由奥斯本等人描述。[3]然后由斯特赖克等人开发为有用的合成工具。[4]尽管斯特赖克试剂有许多应用，但一些研究集中在较低核的氢化铜络合物的合成上。huang等人[5]报道了三核（μ 3-H）双阳离子配合物A的合成和X射线晶体结构（<图1）。Caulton等人[6]试图产生一个单核四配位CuI配合物含有一个终端氢化物，但获得和晶体学特征的双核配合物B类型[L2 CuH] 2。最近，Lipshutz et al. [7]制备了以双齿（R）-DTBM-segphos配体为特征的配合物C。[8]这种三配位单核复合物非常稳定，因为如果在氩气下保存，它可以在室温下在溶液中储存数周;然而，它仅通过对应于δ = 2.55ppm处的氢化物的1H NMR信号在光谱上被鉴定。在过去的几年中，已经表明N-杂环卡宾（NHC）能够稳定高活性主基物种，[9]还有低配位金属中心。[10使用此属性，Sadighi et al. [12]报道了二聚（NHC）氢化铜络合物D的制备。作者指出，这种络合物"有些不稳定，在环境温度下在溶液中持续足够长的时间，以允许容易地记录其1H NMR光谱，但在溶液中1小时后或在固体形式下几天后分解得相当多"。然而，尽管它不稳定，他们设法在非常小的规模获得适合X射线衍射的单晶。注意，Nolan等人报道了非常相似的（NHC）CuH络合物的1H NMR。[13]但被描述为太不稳定而不能分离。
Discovered as early as 1844,[1] copper (I) hydride complexes have attracted considerable interest. In combination with a hydrosilane, as a hydride source, they promote the hydrosilylation of ketones and aldehydes, and they are efficient catalysts in the regioselective conjugate reduction of a number of carbonyl derivatives, including unsaturated ke-tones, aldehydes, and esters.[2] The most extensively studied copper hydride is certainly the hexameric [(Ph3P) CuH] 6, first described by Osborn et al.[3] and then developed as a useful synthetic tool by Stryker et al.[4] Despite the numerous applications of the Stryker reagent, several studies have focused on the synthesis of copper hydride complexes of lower nuclearity. Huang et al.[5] reported the synthesis and X-ray crystal structure of the trinuclear (μ3-H) dicationic complex A (< Figure 1). Caulton et al.[6] attempted to generate a mononuclear four-coordinate CuI complex containing a terminal hydride, but obtained and crystallographically characterized the dinuclear complex B of type [L2CuH] 2. More recently, Lipshutz et al.[7] have prepared complex C featuring the bidentate (R)-DTBM-segphos ligand.[8] This tricoordinate mononuclear complex is exceptionally stable since it can be stored in solution for weeks at room temperature, if kept under argon; however, it has only been spectroscopically identified by a 1H NMR signal corresponding to the hydride at δ= 2.55 ppm.In the last few years, it has been shown that N-heterocyclic carbenes (NHCs) were able to stabilize highly reactive main-group species,[9] and also low-coordinate metal centers.[10, 11] Using this property, Sadighi et al.[12] reported the preparation of the dimeric (NHC) copper hydride complex D. The authors stated that this complex “is somewhat unstable, persisting long enough in solution at ambient temperature to permit the easy recording of its 1H NMR spectrum but decomposing considerably after 1 h in solution or after several days in the solid form”. However, despite its instability, they managed on a very small scale to obtain single crystals suitable for X-ray diffraction. Note that the 1H NMR of a very similar (NHC) CuH complex was reported by Nolan et al.[13] but described as too unstable to be isolated.
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影响因子：
16.6
作者：
Lavallo, V;Canac, Y;Bertrand, G
通讯作者：
Bertrand, G
影响因子：
2.8
作者：
Mankad, NP;Laitar, DS;Sadighi, JP
通讯作者：
Sadighi, JP
影响因子：
2
作者：
Lipshutz, Bruce H.
通讯作者：
Lipshutz, Bruce H.
影响因子：
16.6
作者：
Lipshutz, BH;Frieman, BA
通讯作者：
Frieman, BA
影响因子：
4.9
作者：
Gaillard, Sylvain;Slawin, Alexandra M. Z.;Nolan, Steven P.
通讯作者：
Nolan, Steven P.