The first boron-bridged [1]ferrocenophanes, Fe(η-C5H4)2BN(SiMe3)2 (4a), Fe(η-C5H4)2BN(tBu)SiMe3 (4b), and Fe(η-C5H4)2BNiPr2 (4c), have been synthesized via reaction of Fe(η-C5H4Li)2·nTMEDA (TMEDA = N,N,N‘,N‘-tetramethylethylenediamine) with the aminodichloroboranes Cl2BN(SiMe3)2, Cl2BN(tBu)SiMe3, and Cl2BNiPr2, respectively. Species 4a, 4b, and 4c represent the first [1]ferrocenophanes containing a bridging first row element and were isolated in 35−44% yield as dark red crystalline solids which were characterized by multinuclear NMR and UV−vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction (4a,c). The tilt-angle between the planes of the cyclopentadienyl rings in 4a and 4c was found to be 32.4(2)° and 31.2(2)° (average), respectively. The angle of 32.4(2)° in 4a represents the largest tilt reported to date for any [n]ferrocenophane. The ring-tilting results in a considerable redshift of the lowest energy absorbances in the UV−vis spectra recorded in hexanes (λmax 479 (4a), 489 (4b),...