(η<sup>5</sup>-Pentamethylcyclopentadienyl)rhodium and -iridium Complexes with Weakly and Strongly Coordinating Anions: Isolation and First X-ray Molecular Structures of the Tris(solvent) Complexes [(C<sub>5</sub>Me<sub>5</sub>)M(acetone)<sub>2</sub>(H<sub>2</sub>O)][BF<sub>4</sub>]<sub>2</sub> (M = Rh, Ir)
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Several novel pentamethylcyclopentadienyl complexes of general formula [(C5Me5)IrL3][BF4]2 were prepared including the tris(solvent) precursors [(C5Me5)M(acetone)2(H2O)][BF4]2 (M = Rh, Ir) (1a,b). The X-ray molecular structures of 1a,b were determined at low temperature. Complexes 1a,b are isostructural, and both compounds crystallize in the monoclinic space group P21/c with a = 10.157(3) Å, b = 14.038(9) Å, c = 16.335(2) Å, β = 99.73(2)°, and Z = 4 for 1a and with a = 10.107(9) Å, b = 13.994(16) Å, c = 15.996(34) Å, β = 99.61(12)°, and Z = 4 for 1b. The coordinated water molecule is hydrogen bonded to both BF4- anions. Reaction of 1a,b with pyridine (py) afforded the related tris(pyridine) complexes [(C5Me5)M(η1-(N)-py)3][BF4]2 (M = Rh, Ir) (2a,b). Complex 2b was characterized by X-ray crystallography, monoclinic space group P21/c with a = 8.665(3) Å, b = 19.687(7) Å, c = 18.408(5) Å, β = 94.17(3)°, and Z = 4. Moreover, we prepared the novel neutral compounds (C5Me5)M(η2-NO3)(η1-NO3) (M = Rh, Ir) (4a,b) where the anions are bonded to the metal center instead of a coordinating solvent as confirmed by X-ray study on the iridium complex 4b. The latter crystallizes in the orthorhombic space group Pcab with a = 13.032(4) Å, b = 14.370(11) Å, c = 14.839(18) Å, and Z = 8.
