Hydridoborylene Complexes and Di‐, Tri‐, and Tetranuclear Borido Complexes with Hydride Ligands

Mono‐ and dinuclear hydridoborylene complexes were prepared by intermetallic borylene transfer from Group VI borylene or metalloborylene reagents. The hydride and borylene ligands were found to interact with each other significantly, although the boron ligand retains much of its former borylene character. Zero‐valent platinum fragments were successively added to the dinuclear hydridoborylene complexes, resulting in tri‐ and tetranuclear borido complexes, in which the B? H interaction has been lost, and the hydride ligands now bridge two metal centers. The complexes were studied spectroscopically, crystallographically, and by DFT methods, and the unusual bonding situation in the M? B? H triangles of hydridoborylene complexes were evaluated.