Synthesis and Characterization of a Cu14 Hydride Cluster Supported by Neutral Donor Ligands

The copper hydride clusters [Cu14H12(phen)6(PPh3)4][X]2 (X=Cl or OTf; OTf=trifluoromethanesulfonate, phen=1,10‐phenanthroline) are obtained in good yields by the reaction of [(Ph3P)CuH]6 with phen, in the presence of a halide or pseudohalide source. The complex [Cu14H12(phen)6(PPh3)4][Cl]2 reacts with CO2 in CH2Cl2, in the presence of excess Ph3P, to form the formate complex [(Ph3P)2Cu(κ2‐O2CH)], along with [(phen)(Ph3P)CuCl]. The copper hydride clusters [Cu14H12(phen)6(PPh3)4][X]2 (X=Cl or OTf; OTf=trifluoromethanesulfonate, phen=1,10‐phenanthroline) were obtained in good yields by the reaction of [(Ph3P)CuH]6 with phen, in the presence of a halide or pseudohalide source. This work demonstrates that [(Ph3P)CuH]6 is a viable precursor for the generation of high nuclearity copper clusters.