Metal hydride clusters have historically been studied to unravel their aesthetically pleasing molecular structures and interesting properties, especially toward hydrogen related applications. Central to this work is the hydride ligand, H¯, the smallest closed-shell spherical anion known. Two new developments in polyhydrido nanocluster chemistry include the determination of heretofore unknown hydride coordination modes and novel structural constructs, and conversion from the molecular entities to rhombus-shaped copper nanoparticles (CuNPs). These advances, together with hydrogen evolution and catalysis, have provided both experimentalists and theorists with a rich scientific directive to further explore. The isolation of hexameric [{(Ph3P)CuH}6] (Stryker reagent) could be regarded as the springboard for the recent emergence of polyhydrido copper cluster chemistry due to its utilization in a variety of organic chemical transformations. The stability of clusters of various nuclearity was improved through phosphine, pyridine, and carbene type ligands. Our focus lies with the isolation of novel copper (poly)hydride clusters using mostly the phosphor-1,1-dithiolato type ligands. We found such chalcogen-stabilized clusters to be exceptionally air and moisture stable over a wide range of nuclearities (Cu7 to Cu32). In this Account, we (i) report on state-of-the-art copper hydride cluster chemistry, especially with regards to the diverse and novel structural types generally, and newly discovered hydride coordination modes in particular, (ii) demonstrate the indispensable power of neutron diffraction for the unambiguous assignment and location of hydride ligand(s) within a cluster, and (iii) prove unique transformations that can occur not only between well characterized high nuclearity clusters, but also how such clusters can transform to uniquely shaped nanoparticles of several nanometers in diameter through copper hydride reduction. The increase in the number of low- to high-nuclearity hydride clusters allows for different means by which they can be classified. We chose a classification based on the coordination mode of hydride ligand within the cluster. This includes copper clusters associated with bridging (μ2-H) and capping (μ3-H) hydride modes, followed by an interstitial (μ4-H) hydride mode that was introduced for the first time into octa- and hepta-nuclear copper clusters stabilized by dichalcogen-type ligands. This breakthrough provided a means to explore higher nuclearity polyhydrido nanoclusters, which contain both capping (μ3-H) and interstitial (μ(4-6)-H) hydrides. The presence of bidentate ligands having mixed S/P dative sites led to air- and moisture-stable copper hydride nanoclusters. The formation of rhombus-shaped nanoparticles (CuNPs) from copper polyhydrides in the presence of excess borohydrides suggests the presence of metal hydrides as intermediates during the formation of nanoparticles.
An unprecedented air-stable, nanospheric polyhydrido copper cluster, [Cu20H11(S2P(O(i)Pr)2)9] (1H), which is the first example of an elongated triangular orthobicupola array of Cu atoms having C3h symmetry, was synthesized and characterized. Its composition was primarily determined by electrospray ionization mass spectrometry, and it was fully characterized by (1)H, (2)H, and (31)P NMR spectroscopy and single-crystal X-ray diffraction (XRD). The structure of complex 1H can be expressed in terms of a trigonal-bipyramidal [Cu2H5](3-) unit anchored within an elongated triangular orthobicupola containing 18 Cu atoms, which is further stabilized by 18 S atoms from nine dithiophosphate ligands and six capping hydrides. The positions of the 11 hydrides revealed by low temperature XRD were supported by a density functional theory investigation on the simplified model [Cu20H11(S2PH2)9] with C3h symmetry. 1H is capable of releasing H2 gas upon irradiation with sunlight, under mild thermal conditions (65 °C), or in the presence of acids at room temperature.
An air- and moisture-stable nanoscale polyhydrido copper cluster [Cu32 (H)20 {S2 P(OiPr)2 }12 ] (1H ) was synthesized and structurally characterized. The molecular structure of 1H exhibits a hexacapped pseudo-rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2×9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu32 cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high-resolution neutron diffraction to exhibit tri-, tetra-, and pentacoordinated hydrides in capping and interstitial modes. This result was further supported by a density functional theory investigation on the simplified model [Cu32 (H)20 (S2 PH2 )12 ].
A novel discrete [Ag21{S2P(OiPr)2}12](PF6) nanocluster has been synthesized and characterized by single-crystal X-ray diffraction and also NMR spectroscopy ((1)H, (31)P), ESI mass spectrometry, and other analytic techniques (XPS, EDS, UV/Vis spectroscopy). The Ag21 skeleton has an unprecedented silver-centered icosahedron that is capped by eight additional metal atoms. The whole framework is protected by twelve dithiophosphate ligands. According to the spherical Jellium model, the stability of monocationic nanocluster can be described by an 8-electron superatom with 1S(2) 1P(6) configuration, as confirmed by DFT calculations.
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