Abstract

The synthesis of several titanium-iron multiply bonded complexes supported by a 2-(diphenylphosphino)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(μ2-NP)4Fe, 2. X-ray crystallographic analysis reveals a short metal-metal distance (2.021(2) and 2.028(2)Å 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, [K2][(κ1-NP)Ti(μ2-NP)3Fe], 3, where one phosphine arm has decoordinated from Fe, and the Fe-Ti triple bond has shortened to 1.9474(7)Å. This shortening results from the local ligand field change about Fe from tetragonal to trigonal, which allows for significantly better orbital overlap with Ti.

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