Multimetallic systems composed of CpFe(CO) 2 -, Cp 2 Re- and (RCO 2 ) 2 Bi- moieties

Abstract The reaction of [Fp] 2 (Fp = ( η 5 -C 5 H 5 )(CO) 2 Fe) with bismuth formate was shown to proceed via Fe-Bi bond formation yielding [Fp–Bi(O 2 CH) 2 ] n , 1 , that could be crystallized in form of two polymorphs. These differ in the way the [Fp−Bi(O 2 CH) 2 ] units are connected via bridging formate ligands to yield the respective coordination polymers. The acetate derivative [Fp–Bi(O 2 CCH 3 ) 2 ] was used as a precursor compound targeting at the construction of an additional transition metal-bismuth bond: the reaction of [Fp–Bi(O 2 CCH 3 ) 2 ] with [Cp 2 ReH] likely yields in the envisaged complex [Fp−Bi(O 2 CCH 3 )ReCp 2 ] first but then undergoes further transformation due to the presence of chloride and acetic acid in solution, which lead to the formation of [Fp−Bi(Cl)ReCp 2 ], 3 , and [Cp 2 Re–Bi(O 2 CCH 3 ) 2 ], 4 , respectively. The identity of the heterotrimetallic compound 3 was established by a single-crystal X-ray diffraction analysis, while an independent synthetic route (reaction of [Cp 2 ReH] with [Bi(O 2 CCH 3 ) 3 ]) was developed for 4 in order to unambiguously identify 4 also as the product of the reaction between [Fp–Bi(O 2 CCH 3 ) 2 ] and [Cp 2 ReH].