Selective ring-opening reactions of

Abstract

The reactivity of strained [1]ferrocenophanes, [Fe(eta-C5H4)2ERx] (ERx = SiMe2, 1a: SiMePh, 1b; SnR2, 1c), towards boron halides has been investigated and has been shown to provide a facile pathway to ferrocene derivatives functionalized with Lewis acidic boron centers. The boron halides RBX2 (R = Cl, Ph, fc; X = Cl, Br) (fc = Fe(eta-C5H4)2) lead to selective cleavage of the Si-Cp bonds in 1a and 1b to give, depending on the reaction stoichiometry, functionalized mono- or diferrocenylboranes RnB [(eta-C5H4)Fe(eta-C5H4SiMe2Cl)](3-n) (2a: R = Cl, n = 2; 2b: R = Cl, n = 1; 2c: R = Ph, n = 1) and RnB[(eta-C5H4)Fe(eta-C5H4SiMePhCl)](3-n) (2d: R = Cl, n = 2) in high yields. Compounds 2a-d were characterized by multinuclear NMR spectroscopy, mass spectrometry, and by single-crystal X-ray diffraction (for 2b). Most likely due to steric constraints, a triferrocenylborane was not obtained even from the reaction of BCl3 with an excess of 1a, whereas facile formation of the diferrocenylphenylborane 2c from PhBCl2 and two equivalents of 1a was observed. Selective hydrolysis of the B-Cl bonds of chlorodiferrocenylborane 2b in the presence of trace amounts of water led to the silylated tetranuclear ferrocene complex [(ClMe2Sifc)2B-O-B(fcSiMe2Cl)2] (3) without cleavage of the Si-Cl bonds. The structure of 3 was confirmed by an X-ray diffraction study. Studies of the reactivity of the higher Group 14 homologue of 1a and 1b, the tin-bridged [1]ferrocenophane 1c, revealed that facile addition of B-Cl bonds occurs across the Sn-Cp bonds to yield the 1-stannyl-1'-borylferrocenes [(ClMes2Sn)fc(BClR)] (4a: R = Cl; 4b: R = Ph; Mes = 2,4,6-Me3C6H2). The new synthetic methodology can be extended to bifunctional Lewis acids such as the bis(boryl)ferrocene 1,1'-fc(BBr2)2, which affords the linear boron-bridged ferrocene trimer 1,1'-[fc[B(Br)fcSiMe2Br]2] 5 in 54% isolated yield. In order to incorporate the functionalized ferrocenylboranes into polymer structures, compound 2c was reduced with Li[BEt3H] to give the silicon-hydride functionalized species [PhB[(eta-C5H4)Fe(eta-C5H4SiMe2H)]2] (6), which was then used as a capping reagent in the transition metal catalyzed polymerization of 1a. This process leads to the incorporation of the ferrocenylborane unit into the main chain of a poly(ferrocenylsilane) to afford [PhB-[(fcSiMe2)(n-1)fcSiMe2H]2] (7).