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Low-Coordinate Iron(I) and Manganese(I) Dimers: Kinetic Stabilization of an Exceptionally Short Fe[BOND]Fe Multiple Bond


  • We thank the Australian Research Council (C.J. and K.S.M.) and the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-11-1-4110 to C.J.). L.G. and S.L. thank the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program for support (USDOE/DE-SC002183). The EPSRC is also thanked for access to the UK National Mass Spectrometry Facility. Nicholas Chilton (Monash) is thanked for carrying out D calculations.


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Not just any old iron! The reduction of a bulky guanidinato iron(II) bromide complex yields a three-coordinate iron(I) dimer that possesses the shortest Fe–Fe interaction (2.127 Å) reported to date. Magnetic, Mössbauer, and computational studies show the unprecedented compound to contain two high-spin iron(I) centers with significant multiple-bond character. A related dimer containing a rare example of an unsupported, carbonyl-free Mn[BOND]Mn bond is also described.