Synthesis, spectroscopic and structural characterization of the first mixed fluoro‐bromo group 4 organometallic complex [{Cp*ZrF 2 Br} 4 ] (Cp* = C 5 Me 5 )

[{Cp*ZrF 2 Br} 4 ] is conveniently prepared in high yield from the reaction of [{Cp*ZrF 3 } 4 ] with four equivalents of Me 3 SiBr. In contrast the reaction of [{Cp*ZrF 3 } 4 ] with Me 3 SiI under identical reaction conditions leads to a mixture of [Cp*ZrI 3 ] and unreacted [{Cp*ZrF 3 } 4 ]. The crystal structure of [{Cp*ZrF 2 Br} 4 ] has been determined by X‐ray diffraction studies. The compound crystallizes in the orthorhombic crystal system [a = 9.325(1), b = 23.483(3), c = 27.016(5) Å, α = β = γ = 90°, space group Ibam, Z = 4]. The tetrameric core structure of [{Cp*ZrF 2 Br} 4 ] contains four zirconium atoms linked by alternating single and triple fluorine bridges. One terminal bromine atom is bonded to each zirconium. 1 H and 19 FNMR spectroscopic data and structural features of the title compound are compared with those for the mixed fluoro‐chloro complexes [{Cp*ZrF 2 Cl} 4 ], [{Cp*ZrF 2 Cl} 2 {Cp*ZrFCl 2 } 2 ] and the trifluoro complex [{Cp*ZrF 3 } 4 ].