3 years ago

Substitution reactions of diiron diselenolato complex with bisphosphine ligands

Qian-li Li, Shuang Lü, Ru-fen Zhang, Dong Zhao, Chun-lin Ma

Publication date: Available online 7 January 2019

Source: Polyhedron

Author(s): Qian-Li Li, Shuang Lü, Ru-Fen Zhang, Dong Zhao, Chun-Lin Ma

Abstract

The reactions of (µ-PhCH2Se)2Fe2(CO)6 (A) with the bisphosphine ligands [L = Ph2PCH2PPh2 (dppm), cis-Ph2PC2H2PPh2 (dppv), and (Ph2P)2N(n-Pr) (dppn) under various experimental conditions have been studied. Reaction of A with dppm and Me3NO in MeCN at room temperature to give (µ-PhCH2Se)2Fe2(CO)5(k-dppm) (1), where only one phosphorus atom of dppm is coordinated in a monodentate fashion to Fe2Se2 unit. Reaction of A with dppv and Me3NO in toluene/MeCN at room temperature to give (µ-PhCH2Se)2Fe2(CO)4(k2-dppv) (2), where two phosphorus atoms of dppv are chelated to a single iron. While the (µ-PhCH2Se)2Fe2(CO)4(µ-dppm) (3) and (µ-PhCH2Se)2Fe2(CO)4(µ-dppn) (4) can be prepared by treatment of A with 1 equiv of dppm or dppn in refluxing xylene, where the phosphine acts as a bidentate ligand. Interestingly, the C-Se bond homolysis is detected in the reaction of A with dppn, and unexpected dppn-bridged complex (µ-Se)2Fe2(CO)4(µ-dppn) (5) is isolated. All the complexes were characterized by elemental analysis, FT-IR, NMR spectroscopy, as well as by X-ray diffraction analyses.

Graphical abstract

In this work, we found the reaction of (µ-PhCH2Se)2Fe2(CO)6 (A) with the bisphosphine ligands can get different types of carbonyl substituted model complexes, depending on reaction conditions and the structure of the phosphine ligands. It is interesting to find that C-Se bond homolysis is detected in the reaction of A with dppn in refluxing xylene.

Graphical abstract for this article

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