Proximity enforced oxidative addition of a strong unpolar σ-Si-Si bond at rhodium(i).

The new bidentate bisphosphino ligand (5-Ph2P-Ace-6-SiMe2)2 (1) binds rhodium(i) chloride and brings it into close proximity to a strong unpolar σ-Si-Si bond, in which it immediately inserts. In the spirocyclic Rh(iii) product of the oxidative addition, (5-Ph2P-Ace-6-SiMe2)2RhCl (2), the two Si atoms are still close enough to engage in weak non-covalent interactions.

Proximity Enforced Agostic Interactions Involving Closed-Shell Coinage Metal Ions.

A proximity enforcing diarylsilane ligand is reported, which gives rise to unusual Si-H···M interactions with the d10 metal ions Cu+ and Ag+ upon complexation. These interactions are studied in detail both experimentally and computationally and can be classified to be weakly agostic in nature for the Si-H···Cu interaction. The Si-H···Ag interaction has more signatures of an electrostatic contact.