Versatile Fe–Sn Bonding Interactions in a Metallostannylene System: Multiple Bonding and C–H Bond Activation
Rex C. Handford, Mark A. Nesbit, Patrick W. Smith, R. David Britt, T. Don Tilley
Abstract
The metallostannylene Cp*(iPr2MeP)(H)2Fe-SnDMP (1; Cp* = η5-C5Me5; DMP = 2,6-dimesitylphenyl), formed by hydrogen migration in a putative Cp*(iPr2MeP)HFe[Sn(H)DMP] intermediate, serves as a robust platform for exploration of transition-metal main-group element bonding and reactivity. Upon one-electron oxidation, 1 expels H2 to generate the coordinatively unsaturated [Cp*(iPr2MeP)Fe═SnDMP][B(C6F5)4] (3), which possesses a highly polarized Fe–Sn multiple bond that involves interaction of the tin lone pair with iron. Evidence from EPR and 57Fe Mössbauer spectroscopy, along with DFT studies, shows that 3 is primarily an iron-based radical with charge localization at tin. Upon reduction of 3, C–H bond activation of the phosphine ligand was observed to produce Cp*HFe(κ2-(P,Sn)═Sn(DMP)CH2CHMePMeiPr) (5). Complex 5 was also accessed via thermolysis of 1, and kinetics studies of this thermolytic pathway indicate that the reductive elimination of H2 from 1 to produce a stannylyne intermediate, Cp*(iPr2MeP)Fe[SnDMP] (A), is likely rate-determining. Evidence indicates that the production of 5 proceeds through a concerted C–H bond activation. DFT investigations suggest that the transition state for this transformation involves C–H cleavage across the Fe–Sn bond and that a related transition state where C–H bond activation occurs exclusively at the tin center is disfavored, illustrating an effect of iron–tin cooperativity in this system.