The in situ prepared dilithio derivative of the known species 1-bromo-1'-(trimethylsilylamino)ferrocene (I) reacted with tBuPCl(2) to form the first example of a [2]ferrocenophane ([2]FCP) bridged by nitrogen and phosphorus (2). Sulfurization of 2 followed by column chromatography on silica gel gave the expected [2]FCP with a tBu(S)PN(SiMe3) bridging moiety (3a) and its desilylated counterpart with a tBu(S)PNH bridging moiety (3b). The molecular structure of 3b was determined by single-crystal Xray analysis (alpha = 18.40(11)degrees). Using a common synthetic methodology, two new 1-amino-1'-bromoferrocene derivatives were prepared, one species with a PhCH2 (6a) and another with a tBuCH(2) group (6b) on nitrogen. Dilithiation of 6a followed by addition of tBuPCl(2) gave a mixture of three constitutional isomers: the targeted [2]FCP (7a), the 1,1'-disubstituted ferrocene derivative (tBuPH)(PhCH=N)fc (8a), and the [3]FCP bridged by a (NH)(CHPh)PtBu moiety (9a). NMR spectroscopy revealed that 8a is the precursor for 9a. The salt-metathesis reaction of the dilithio derivative of 6b with tBuPCl(2) exclusively gave the 1,1'-disubstituted ferrocene derivative (tBuPH)(tBuCH=N)fc (8b), which does not isomerize to the respective [3]FCP. DFT calculations at the M06/6-311+G(d,p) level were used to better rationalize these unexpected results.