Heterobimetallic complexes containing Ca-Fe or Yb-Fe bonds: synthesis and molecular and electronic structures of [M{CpFe(CO)2}2(THF)3]2 (M = Ca or Yb)

Matthew P Blake; Nikolas Kaltsoyannis; Philip Mountford

doi:10.1021/ja207487j

Heterobimetallic complexes containing Ca-Fe or Yb-Fe bonds: synthesis and molecular and electronic structures of [M{CpFe(CO)2}2(THF)3]2 (M = Ca or Yb)

J Am Chem Soc. 2011 Oct 5;133(39):15358-61. doi: 10.1021/ja207487j. Epub 2011 Sep 12.

Authors

Matthew P Blake¹, Nikolas Kaltsoyannis, Philip Mountford

Affiliation

¹ Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK.

PMID: 21888401
DOI: 10.1021/ja207487j

Abstract

Reaction of calcium or ytterbium amalgam with [CpFe(CO)(2)](2) (Fp(2)) gave the isostructural heavy alkaline earth or divalent rare earth compounds [MFp(2)(THF)(3)](2) (M = Ca or Yb) containing two direct Ca-Fe (3.0185(6) Å) or Yb-Fe (2.9892(4) Å) bonds. Density functional theory supports experiment in finding shorter Yb-Fe than Ca-Fe distances, and Ziegler-Rauk, molecular orbital, and atoms-in-molecules analyses find the M-Fe bonding to be predominantly electrostatic in nature. The Yb-Fe interaction energy and bond critical point electron density are slightly larger than for Ca-Fe, in agreement with the shorter M-Fe bond in the former. The corresponding reaction for magnesium gave MgFp(2)(THF)(4) with two O-bound Fp moieties and no Mg-Fe bond.