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Reaction of [CuH(PPh3)]6 with 1 equiv. of Tl(OTf) results in formation of [Cu6TlH6(PPh3)6][OTf] ([1]OTf]), which can be isolated in good yields. Variable‐temperature 1H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl−H orbital interaction. According to DFT, the 1H chemical shift of the Tl‐adjacent hydride ligands of [1]+ includes 7.7 ppm of deshielding due to spin‐orbit effects from the heavy Tl atom. This study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl−H interaction. [ABSTRACT FROM AUTHOR]

The copper hydride clusters [Cu14 H12 (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 Ph3 P, to form the formate complex [(Ph3P)2Cu(κ(2)-O2CH)], along with [(phen)(Ph3 P)CuCl].

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]. [ABSTRACT FROM AUTHOR]