Protonation of Dppbz- and Binap-Ligated Rhodathiaboranes Yielding Hydron, Hydride, and Hydrogen Exchange.

The reaction of the 11-vertex rhodathiaborane [8,8,8-(H)(PPh)-3-(NCH)--7,8-RhSBH] () with 1,2-bis(diphenylphosphine)benzene (dppbz) and ()-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) affords [1,1-(η-dppbz)-3-(NCH)--1,2-RhSBH] () and [1,1-(η-binap)-3-(NCH)--1,2-RhSBH] (). These 11-vertex -rhodathiaborane chelates result from PPh ligand substitution at the rhodium center and a -to- structural cluster transformation driven by H loss. Treating compounds and with triflic acid (TfOH) leads to the formation of cationic clusters and .