Copper-hydrides have been intensively studied for a long time due to their utilization in a variety of technologically important chemical transformations.Nevertheless,poor stability of the species severely hinders its...Copper-hydrides have been intensively studied for a long time due to their utilization in a variety of technologically important chemical transformations.Nevertheless,poor stability of the species severely hinders its isolation,storage and operation,which is worse for nano-sized ones.We report here an unprecedented strategy to access to ultrastable copper-hydride nanoclusters(NCs),namely,using bidentate N-heterocyclic carbenes as stabilizing ligands in addition to thiolates.In this work,a simple synthetic protocol was developed to synthesize the first large copper-hydride nanoclusters(NCs)stabilized by N-heterocyclic carbenes(NHCs).The NC,with the formula of Cu3i(RS)25(NHC)3H6(NHC=1,4-bis(1-benzyl-1 H-benzimidazol-1-ium-3-yl)butane,RS=4-fluorothiophenol),was fully characterized by high resolution Fourier transform ion cyclotron resonance mass spectrum,nuclear magnetic resonance,ultra-violet visible spectroscopy,density functional theory(DFT)calculations and single-crystal X-ray crystallography.Structurally,the title cluster exhibits unprecedented Cu4 tetrahedron-based vertex-sharing(TBVS)superstructure(fusion of six Cu4 tetrahedra).Moreover,the ultrahigh thermal stability renders the cluster a model system to highlight the power of NHCs(even other carbenes)in controlling geometrical,electronic and surface structure of polyhydrido copper clusters.展开更多
基金the National Key R&D Program of China(No.2017YFA0207302)the National Natural Science Foundation of China(Nos.21890752,21731005,21420102001,and 21721001)and the 111 Project(No.B08027)for financial supportsupported by the Academy of Finland through HHs Academy Professorship and grants 292352,319208.
文摘Copper-hydrides have been intensively studied for a long time due to their utilization in a variety of technologically important chemical transformations.Nevertheless,poor stability of the species severely hinders its isolation,storage and operation,which is worse for nano-sized ones.We report here an unprecedented strategy to access to ultrastable copper-hydride nanoclusters(NCs),namely,using bidentate N-heterocyclic carbenes as stabilizing ligands in addition to thiolates.In this work,a simple synthetic protocol was developed to synthesize the first large copper-hydride nanoclusters(NCs)stabilized by N-heterocyclic carbenes(NHCs).The NC,with the formula of Cu3i(RS)25(NHC)3H6(NHC=1,4-bis(1-benzyl-1 H-benzimidazol-1-ium-3-yl)butane,RS=4-fluorothiophenol),was fully characterized by high resolution Fourier transform ion cyclotron resonance mass spectrum,nuclear magnetic resonance,ultra-violet visible spectroscopy,density functional theory(DFT)calculations and single-crystal X-ray crystallography.Structurally,the title cluster exhibits unprecedented Cu4 tetrahedron-based vertex-sharing(TBVS)superstructure(fusion of six Cu4 tetrahedra).Moreover,the ultrahigh thermal stability renders the cluster a model system to highlight the power of NHCs(even other carbenes)in controlling geometrical,electronic and surface structure of polyhydrido copper clusters.
