期刊
INORGANICA CHIMICA ACTA
卷 460, 期 -, 页码 43-48出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2016.10.002
关键词
Metal-metal multiple bonds; Titanium complexes; Iron complexes; Pyrrolide ligands; Inorganic synthesis
资金
- University of Minnesota
- ACS Petroleum Research Fund [ACS-PRF 54225-DNI3]
- NSF/MRI [1224900]
- NIH [S10OD011952]
- National Science Foundation [00039202]
The synthesis of several titanium-iron multiply bonded complexes supported by a 2-(diphenylphos-phino) pyrrolide (NP) ligand is reported. Treatment of the homoleptic, 8-coordinate Ti(NP)(4) monometallic precursors with FeCl2 and KC8 yielded the tetragonally-symmetric heterobimetallic complex Ti(mu(2)-NP)(4)Fe, 2. X-ray crystallographic analysis reveals a short metal-metal distance (2.021(2) and 2.028(2) angstrom for two independent molecules in the asymmetric unit) consistent with a Fe-Ti triple bond. Theoretical calculations also indicate 3 bonding interactions. Further reduction of 2 by 2 electrons with KC8 results in the isolation of the dianion, [K-2][(kappa(1)-NP)Ti(mu(2)-NP)(3)Fe], 3, where one phosphine arm has decoordinated from Fe, and the Fe-Ti triple bond has shortened to 1.9474(7) angstrom. This shortening results from the local ligand field change about Fe from tetragonal to trigonal, which allows for significantly better orbital overlap with Ti. (C) 2016 Elsevier B.V. All rights reserved.
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