A versatile synthetic protocol is described for the synthesis of heteroatom-bridged biferrocene derivatives, including the symmetric species 2-SnSn and the planar-chiral species 2-SnSi, 2-BSi, and 2-SnP. Treatment of (pR,SS)-2-lithio-1-(p-tolylsufinyl)-ferrocene with 0.5 equiv of Me2SnCl2 afforded the tin-bridged biferrocene 1-Sn. A second Sn, Si, or P bridge was then incorporated by substitution of the sulfinyl group in the ortho-position with a dimethylstannyl, dimethylsilyl, or tert-butylphosphino group, respectively, to give the doubly bridged biferrocenes 2-SnSn, 2-SnSi, and 2-SnP. The dimethylstannyl moiety of 2-SnSi was subsequently replaced with a borane bridge via a two-step transmetalation procedure comprising treatment with HgCl2, followed by PhBCl2. The formation of ferrocene-fused six-membered heterocycles was confirmed by multinuclear NMR spectroscopy and high-resolution MS analyses. The stereochemical configuration of the chiral biferrocenes 2-SnSi, 2-SnP, and 2-BSi was studied by single-cr...