Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 5, Pages 1842-1855Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja409016w
Keywords
-
Categories
Funding
- NSF-MRI [CHE-1229400]
- National Science Foundation (NSF) through the MRSEC Program
- NSF [CHE-1254621, CHE-1212575]
- Alfred Sloan Foundation
- NSF/DOE [CHE-0822838]
- U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1346572, 0822838] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1229400, 1212575, 1254621] Funding Source: National Science Foundation
Ask authors/readers for more resources
A multidentate ligand platform is introduced that enables the isolation of both homo- and heterobimetallic complexes of divalent first-row transition metal ions such as Mn(II), Fe(II), and Co(II). By means of a two-step metalation strategy, five bimetallic coordination complexes were synthesized with the general formula M1M2Cl(py(3)tren), where py(3)tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. The metal-metal pairings include dicobalt (1), cobalt-iron (2), cobalt-manganese (3), diiron (4), and iron-manganese (5). The bimetallic complexes have been investigated by X-ray diffraction and X-ray anomalous scattering studies, cyclic voltammetry, magnetometry, Mossbauer spectroscopy, UV-vis-NIR spectroscopy, NMR spectroscopy, combustion analyses, inductively coupled plasma optical emission spectrometry, and ab initio quantum chemical methods. Only the diiron chloride complex in this series contains a metal-metal single bond (2.29 angstrom). The others show weak metal-metal interactions (2.49 to 2.53 angstrom). The diiron complex is also distinct with a septet ground state, while the other bimetallic species have much lower spin states from S = 0 to S = 1. We propose that the diiron system has delocalized metal-metal bonding electrons, which seems to correlate with a short metal-metal bond and a higher spin state. Multiconfigurational wave function calculations revealed that, indeed, the metal-metal bonding orbitals in the diiron complex are much more delocalized than those of the dicobalt analogue.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available