The reaction of [{Rh(C₅Me₅)}₂(µ-L)(µ-OMe)₂]BF₄[L = pyrazolate (pz), 3-methylpyrazolate, 3,5-dimethylpyrazolate or 3(5)-bromo-5(3)-methylpyrazolate] with HPPh₂ has been studied. Complexes of general formulae [{Rh(C₅Me₅)}₂(µ-L)(µ-OH)(µ-PPh₂)]BF₄, [{Rh(C₅Me₅)}₂(µ-L)(µ-PPh₂)₂]BF₄ and [{Rh(C₅Me₅)}₂(µ-OH)₂(µ-PPh₂)]BF₄ were prepared and characterized by analytical and spectroscopic means. The crystal structure of [{Rh(C₅Me₅)}₂(µ-pz)(µ-PPh₂)₂] BF₄·CHCl₃ was determined. The rhodium atoms show pseudo-octahedral geometry and are separated by 3.473(1)Å. The µ-hydroxo complexes [{Rh(C₅Me₅)}₂(µ-L)(µ-OH)(µ-PPh₂)] BF₄ react with hydrochloric acid affording the corresponding µ-chloride compounds [{Rh(C₅Me₅)}₂(µ-L)(µ-Cl)(µ-PPh₂)] BF₄, which in turn have been also prepared from [{Rh(C₅Me₅)}₂(µ-OH)₃] BF₄, HL, HPPh₂ and HCl in 1 : 1 : 1 : 1 ratio. The crystal structure of [{Rh(C₅Me₅)}₂(µ-pz)(µ-Cl)(µ-PPh₂)] BF₄·CHCl₃ has been determined. Two (C₅Me₅)Rh moieties are connected by three different anionic ligands, pz, Cl and PPh₂. The rhodium atoms are separated by 3.432(1)Å. Aged solutions of reaction mixtures of [{Rh(C₅Me₅)}₂(µ-L)(µ-OMe)₂] BF₄ and HPPh₂ contain [{Rh(C₅Me₅)}₂(µ-Ph₂PO₂)₂(µ-PPh₂)] BF₄, the diphenylphosphinato ligands arising from Ph₂P(O)OH, an oxidation product of HPPh₂. The crystal structure of the solvate has been established. Two Ph₂PO₂ groups and a PPh₂ ligand bridge two (C₅Me₅) Rh units. The rhodium–rhodium distance is 4.049(1)Å. The µ-hydrido complex [{Rh(C₅Me₅)}₂(µ-H)(µ-pz)(µ-PPh₂)] has been prepared by treating [{Rh(C₅Me₅)}₂(µ-OH)₃] BF₄ with Hpz and HPPh₂ in refluxing propan-2-ol.