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Ligand Protonation Triggers H2 Release from a Dinickel Dihydride Complex to Give a Doubly “T”‐Shaped Dinickel(I) Metallodiradical
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-10-07 , DOI: 10.1002/anie.202011494 Peng-Cheng Duan 1, 2 , Roland Alexander Schulz 1 , Anton Römer 3 , Benjamin E Van Kuiken 4, 5 , Sebastian Dechert 1 , Serhiy Demeshko 1 , George E Cutsail 4 , Serena DeBeer 4 , Ricardo A Mata 3 , Franc Meyer 1, 6
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-10-07 , DOI: 10.1002/anie.202011494 Peng-Cheng Duan 1, 2 , Roland Alexander Schulz 1 , Anton Römer 3 , Benjamin E Van Kuiken 4, 5 , Sebastian Dechert 1 , Serhiy Demeshko 1 , George E Cutsail 4 , Serena DeBeer 4 , Ricardo A Mata 3 , Franc Meyer 1, 6
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The dinickel(II) dihydride complex (1K) of a pyrazolate‐based compartmental ligand with β‐diketiminato (nacnac) chelate arms (L−), providing two pincer‐type {N3} binding pockets, has been reported to readily eliminate H2 and to serve as a masked dinickel(I) species. Discrete dinickel(I) complexes (2Na, 2K) of L− are now synthesized via a direct reduction route. They feature two adjacent T‐shaped metalloradicals that are antiferromagnetically coupled, giving an S=0 ground state. The two singly occupied local 
type magnetic orbitals are oriented into the bimetallic cleft, enabling metal–metal cooperative 2 e− substrate reductions as shown by the rapid reaction with H2 or O2. X‐ray crystallography reveals distinctly different positions of the K+ in 1K and 2K, suggesting a stabilizing interaction of K+ with the dihydride unit in 1K. H2 release from 1K is triggered by peripheral γ‐C protonation at the nacnac subunits, which DFT calculations show lowers the barrier for reductive H2 elimination from the bimetallic cleft.
中文翻译：
配体质子化触发二氢化二镍络合物释放 H2，产生双“T”形二镍 (I) 金属双自由基
据报道，基于吡唑盐的区室配体与 β-二酮亚胺 (nacnac) 螯合臂 (L − ) 的二氢二镍 (II) 络合物 ( 1 K ) 提供了两个钳型 {N 3 } 结合口袋，可轻松消除H 2并用作掩蔽二镍（I）物种。 L -的离散二镍(I)络合物( 2 Na , 2 K ) 现在通过直接还原途径合成。它们具有两个相邻的 T 形金属基团，它们是反铁磁耦合的，给出S = 0 基态。两人单独占据当地 型磁轨道定向到双金属裂隙中，从而实现金属-金属协同 2 e -底物还原，如与 H 2或 O 2的快速反应所示。 X射线晶体学揭示了K +在1 K和2 K中明显不同的位置，表明 K +与二氢化物单元在1 K中存在稳定的相互作用。 H 2从1 K的释放是由 nacnac 亚基的外围 γ-C 质子化触发的，DFT 计算表明降低了双金属裂隙还原 H 2消除的势垒。
更新日期：2020-10-07
type magnetic orbitals are oriented into the bimetallic cleft, enabling metal–metal cooperative 2 e− substrate reductions as shown by the rapid reaction with H2 or O2. X‐ray crystallography reveals distinctly different positions of the K+ in 1K and 2K, suggesting a stabilizing interaction of K+ with the dihydride unit in 1K. H2 release from 1K is triggered by peripheral γ‐C protonation at the nacnac subunits, which DFT calculations show lowers the barrier for reductive H2 elimination from the bimetallic cleft.
中文翻译：
配体质子化触发二氢化二镍络合物释放 H2，产生双“T”形二镍 (I) 金属双自由基
据报道，基于吡唑盐的区室配体与 β-二酮亚胺 (nacnac) 螯合臂 (L − ) 的二氢二镍 (II) 络合物 ( 1 K ) 提供了两个钳型 {N 3 } 结合口袋，可轻松消除H 2并用作掩蔽二镍（I）物种。 L -的离散二镍(I)络合物( 2 Na , 2 K ) 现在通过直接还原途径合成。它们具有两个相邻的 T 形金属基团，它们是反铁磁耦合的，给出S = 0 基态。两人单独占据当地
型磁轨道定向到双金属裂隙中，从而实现金属-金属协同 2 e -底物还原，如与 H 2或 O 2的快速反应所示。 X射线晶体学揭示了K +在1 K和2 K中明显不同的位置，表明 K +与二氢化物单元在1 K中存在稳定的相互作用。 H 2从1 K的释放是由 nacnac 亚基的外围 γ-C 质子化触发的，DFT 计算表明降低了双金属裂隙还原 H 2消除的势垒。
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