The reaction of nonsubstituted alkali metal cyclopentadienides with haloboranes leads to ∼90:10 mixtures of isomeric diene products that can be deprotonated to give simple boryl cyclopentadienides. We extended this transformation to the sterically hindered lithium tert-butylcyclopentadienide 1 using FBMes (Mes = 2,4,6-trimethylphenyl) and ClBCy as electrophiles. The boryl group is selectively introduced in the remote position to minimize steric congestion. The new boryl dienes are obtained as mixtures of isomers, and subsequent deprotonation with MeLi or LiHMDS affords the lithium 1,3-disubstituted cyclopentadienides 5a,b in yields over 95%. Direct assembling of tert-butylated boryl cyclopentadienides with MCl (M = Fe, Co) selectively leads to 1,1'-planar chiral ferrocenes 6a,b and cobaltocene 7. To shed light into the diastereoselective formation of 6a, DFT calculations were performed. The potential energy surface was scrutinized so as to identify and compare its diastereoisomers and conformers. This stereoselectivity is attributed to minimized steric repulsions between the tert-butyl and the BMes groups in the eclipsed conformation of the racemic diastereoisomers. The X-ray structures of boryl diene 2a and diboryl ferrocene 6a are reported. The electronic structure of cobaltocene 7 was analyzed by EPR and DFT calculations. The spin density of this unique open-shell complex is mainly localized on the Co center, but significant spin density is also found on the boron atoms, indicating substantial delocalization of the unpaired electron over the Lewis acid moieties. Consistently, the singly occupied molecular orbital is a combination of a Co-centered 3d orbital with π(BC) orbitals on each CpBMes rings. There is only weak, if any, direct M···B interaction in 6 and 7.

A general synthesis of highly functionalized ferrocenes, which include (P,B)- and (N,B)-ambiphiles, has been developed at a multigram scale. Diastereoselective stepwise modification of di-tert-butylated ferrocenes included the unprecedented separation of electroactive species. Bulky alkyl groups on ferrocenes ensure planar chirality of ambiphiles and enforce closer proximity of antagonist Lewis functions.