Coordination solids derived from Cp*M(CN)3- (M = Rh, Ir)

Solutions of Rh-2(OAc)(4) and Et4N[Cp*Ir(CN)(3)] react to afford crystals of the one-dimensional coordination solid {Et4N[Cp*Ir(CN)(3)][Rh-2(OAc)(4)]}. This reaction is reversed by coordinating solvents such as MeCN. The structure of the polymer consists of helical anionic chains containing Rh-2(OAc)(4) units linked via two of the three CN ligands of Cp*Ir(CN)(3)(-). Use of the more Lewis acidic Rh-2(O2CCF3)(4) in place of Rh-2(OAc)(4) gave purple {(Et4N)(2)[CP*Ir(CN)(3)](2)[Rh-2(O2CCF3)(4)](3)} whose insolubility is attributed to stronger Rh-NC bonds as well as the presence of cross-linking. The species {[Cp*Rh(CN)(3)][Ni(en)(n)](PF6)} (n = 2, 3) crystallized from an aqueous solution of Et4N[Cp*Rh(CN)(3)] and [Ni(en)(3)](PF6)(2); {(Cp*Rh(CN)(3)][Ni(en)(2)](PF6)} consists of helical chains based on cis-Ni(en)(2)(2+) units. Aqueous solutions of Et4N[Cp*Ir(CN)(3))] and AgNO3 afforded the colorless solid {Ag[Cp*Ir-(CN)(3)](2)}. Recrystallization of this polymer from pyridine gave the hemipyridine adduct {Ag[Ag(py)[Cp*Ir- (CN)(3)](2)} The C-13 cross-polarization magic-angle spinning NMR spectrum of the pyridine derivative reveals two distinct Cp* groups, while in the pyridine-free precursor, the Cp*'s appear equivalent. The solid-state structure of (Ag[Ag(py)][Cp*Ir(CN)(3)](2)) reveals a three-dimensional coordination polymer consisting of chains of Cp*Ir(CN)(3)(-)units linked to alternating Ag+ and Ag(py)(+) units. The network structure arises by the linking of these helices through the third cyanide group on each Ir center.