An N‐Heterocyclic Boryloxy Ligand Isoelectronic with N‐Heterocyclic Imines: Access to an Acyclic Dioxysilylene and its Heavier Congeners

Abstract

Introduced here is a new type of strongly donating N-heterocyclic boryloxy (NHBO) ligand, [(HCDippN)₂ BO]^- (Dipp=2,6-diisopropylphenyl), which is isoelectronic with the well-known N-heterocyclic iminato (NHI) donor class. This 1,3,2-diazaborole functionalized oxy ligand has been used to stabilize the first acyclic two-coordinate dioxysilylene and its Ge, Sn, and Pb congeners, thereby presenting the first complete series of heavier group 14 dioxycarbene analogues. All four compounds have been characterized by X-ray crystallography and density-functional theory, enabling analysis of periodic trends: the potential for the [(HCDippN)₂ BO]^- ligand to subtly vary its electronic-donor capabilities is revealed by snapshots showing the gradual evolution of arene π coordination on going from Si to Pb.