om200381p_si_001.cif (19.35 kB)
Structure and Bonding of the Manganese(II) Phosphide Complex (t-BuPH2)(η5-Cp)Mn{μ-(t-BuPH)}2Mn(Cp)(t-BuPH2)
dataset
posted on 2012-01-09, 00:00 authored by Francesca
A. Stokes, Robert J. Less, Joanna Haywood, Rebecca L. Melen, Richard
I. Thompson, Andrew E. H. Wheatley, Dominic S. Wright, Adam Johannes Johansson, Lars KlooRather than achieving bis-deprotonation of the phosphine,
reaction
of Cp2Mn (Cp = cyclopentadienyl) with t-BuPH2 at room temperature yields monodeprotonation of
half of the available phosphine in the product (t-BuPH2)(η5-Cp)Mn{μ-(t-BuPH)}2Mn(Cp)(t-BuPH2) (1). This complex comprises a Mn(II) phosphide and is a dimer
in the solid state, containing a Mn2P2 diamond
core. Consistent with the observation of a relatively short intermetal
distance of 2.8717(4) Å in 1, DFT analysis of the
full structure points to a singlet ground state stabilized by a direct
Mn–Mn single bond. This is in line with the diamagnetic character
of 1 and an 18-electron count at Mn.
