Low-nuclearity copper hydrides are rare and few well-defined dicopper hydrides have been reported. Herein, we describe the first example of a structurally characterized anionic dicopper hydride complex. This complex does not display typical reactivity associated with low-nuclearity copper hydrides, such as alcoholysis or insertion reactions. Instead, its stoichiometric and catalytic reactivity is akin to that of copper hydride clusters. The distinct reactivity is ascribed to the robust dinuclear core that is bound tightly within the dinucleating ligand scaffold.

Steric properties of ligands are an important parameter for tuning the reactivity of the corresponding complexes. For various ligands used in mononuclear complexes, methods have been developed to quantify their steric bulk. In this work, we present an expansion of the buried volume and the G-parameter to quantify the steric properties of 1,8-napthyridine-based dinuclear complexes. Using this methodology, we explored the tunability of the steric properties associated with these ligands and complexes.

Activation of a Si–H bond is commonly a critical step in catalytic hydrosilylation reactions. Herein, we investigate the cooperative reactivity of Ni(0) centers bearing a side-bound imine ligand toward silanes. Such complexes activate a Si–H bond of diphenylsilane, resulting in formal hydrosilylation of the imine backbone, which acts as a hydride acceptor. The resulting hydrosilazane motif engages either in coordination to nickel via the Si–H bond, forming an 18-electron η2-Si–H complex, or oxidative addition to Ni to form 16-electron Ni­(II) silyl/hydride complexes. DFT calculations suggest a cooperative activation of the silane via ligand-to-ligand hydride transfer. In addition, the silicon fragment readily exchanges with external hydrosilanes, showing that the Si–N bond can be reversibly cleaved under mild conditions.

Low‐nuclearity copper hydrides are rare and few well‐defined dicopper hydrides have been reported. Herein, we describe the first example of a structurally characterized anionic dicopper hydride complex. This complex does not display typical reactivity associated with low‐nuclearity copper hydrides, such as alcoholysis or insertion reactions. Instead, its stoichiometric and catalytic reactivity is akin to that of copper hydride clusters. The distinct reactivity is ascribed to the robust dinuclear core that is bound tightly within the dinucleating ligand scaffold.

Steric properties of ligands are an important parameter for tuning the reactivity of the corresponding complexes. For various ligands used in mononuclear complexes, methods have been developed to quantify their steric bulk. In this work we present an expansion of the buried volume and G-parameter to quantify the steric properties of 1,8-napthyridine based dinuclear complexes. Using this methodology, we explored the tuneability of the steric properties associated with these ligands and complexes.