Creating Iron– and Rhenium–Bismuth Bonds by Reactions with Organometallic Hydrides

While addition of [Cp 2 ReH] to [Bi(O t Bu) 3 ] leads to an equilibrium containing [Cp 2 Re‐Bi(O t Bu) 2 ], [{Cp 2 Re} 2 Bi(O t Bu)], t BuOH and [CpRe( μ ‐ η 5 , η 1 ‐C 5 H 4 )Bi–ReCp 2 ], in the presence of water [{(Cp 2 Re) 2 Bi} 2 O] ( 1 ) is formed selectively. Also [FpH] [Fp = ( η 5 ‐C 5 H 5 )(CO) 2 Fe] can be employed as a precursor to form heterometallic bismuth compounds. Synthesis of [FpBi{OCH(CF 3 ) 2 } 2 ] 2 ( 5 ) can be achieved by reaction of [FpH] with [Bi{OCH(CF 3 ) 2 } 3 (thf)] 2 and carboxylates [FpBi(O 2 CR) 2 ] 2 are generated upon treatment of [FpH] with [Bi(O 2 C R ) 3 ] ( R = CH 3 , t Bu). While the compounds [Fp‐Bi(O 2 C R ) 2 ] 2 can also be obtained from reactions with Fp‐Fp, they are formed far more readily using [FpH] as the precursor. They typically crystallize as dimers, like the alkoxide 5 . A monomeric compound of the type [Fp‐BiX 2 ] ( 6 ) could be isolated for X = thd (tetramethylheptanedionate), that is, after the reaction of [FpH] with [Bi(thd) 3 ]. Altogether, the results demonstrate the potential of [FpH] as a precursor for [Fp‐Bi X 2 ] compounds, which are formed in reactions with bismuth alkoxides, carboxylates and diketonates.