Comparison of nucleophilic- and radical-based routes to the formation of manganese-main group element single bonds. Issue 20 (9th May 2017)

• Record Type: Journal Article
• Authors: Agnew, Douglas W.; Moore, Curtis E.; Rheingold, Arnold L.; Figueroa, Joshua S.
• Is Part Of: Dalton transactions. Volume 46:Issue 20(2017)
• Page Start: 6700
• Page End: 6707
• Publication Date: 2017-05-09
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt01102d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : One-electron activation of main-group substrates by a stable manganese metalloradical provides a facile pathway to Mn-element single bonds. Abstract : Using the stable metalloradical Mn(CO)3 (CNAr Dipp2 )2, we report the formation of manganese-main group complexes via the single-electron functionalization of main group halides. The reactions occur in a simple 1 : 1 stoichiometry, and demonstrate the utility of using stable open-shelled organometallics as precursors for metal-main group compounds. This has enabled the preparation of manganese complexes bearing terminal –EX n substituents, as shown through the isolation of Mn(SnCl)(CO)3 (CNAr Dipp2 )2 and Mn(BiCl2 )(CO)3 (CNAr Dipp2 )2 from SnCl2 and BiCl3, respectively. Through this approach, we have also isolated Mn(SbF2 )(CO)3 (CNAr Dipp2 )2 from SbF3, which serves as a unique example of a terminal –SbF2 complex. Although the metalloradical functionalization of binary main group halides provides the desired main group adduct in yields comparable to nucleophilic activation using the manganate Na[Mn(CO)3 (CNAr Dipp2 )2 ], the former approach is shown to be far more atom-economical with respect to Mn. Additionally, we have found that Mn(CO)3 (CNAr Dipp2 )2 also serves as a convenient precursor to MnF(CO)3 (CNAr Dipp2 ). The latter is an analogue to the elusive monofluoride FMn(CO)5 .