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Klaus-Dieter Warzecha
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These species usually do not exist in nature, but they can be synthesized.

  1. Silver has been reduced in liquid ammonia to give $\ce{Ag-}$.
  2. A lot of anionic metal carbonyl complexes $\ce{M(CO)_{n}^{m-}}$ have been synthesized:

###-1

  • $\ce{[V(CO)6]-}$, $\ce{[Nb(CO)6]-}$, $\ce{[Ta(CO)6]-}$, $\ce{[Mn(CO)5]-}$, $\ce{[Ir(CO)4]-}$, $\ce{[Co(CO)4]-}$, $\ce{[Rh(CO)4]-}$

-2

  • $\ce{[Ti(CO6)]^{2-}}$, $\ce{[Zr(CO6)]^{2-}}$, $\ce{[Hf(CO6)]^{2-}}$, $\ce{[Fe(CO4)]^{2-}}$, $\ce{[Ru(CO4)]^{2-}}$, $\ce{[Os(CO4)]^{2-}}$

###-3

  • $\ce{[V(CO5)]^{3-}}$, $\ce{[Nb(CO5)]^{3-}}$, $\ce{[Ta(CO5)]^{3-}}$, $\ce{[Mn(CO4)]^{3-}}$, $\ce{[Re(CO4)]^{3-}}$

###-4

  • $\ce{[Cr(CO4)]^{4-}}$, $\ce{[Mo(CO4)]^{4-}}$

There's a review by John E. Ellis: Highly Reduced Metal Carbonyl Anions: Synthesis, Characterization, and Chemical Properties on these compounds.

Klaus-Dieter Warzecha
  • 44.2k
  • 8
  • 104
  • 166