Reactivity of cyclopentadienyl transition metal(II) complexes with borate ligands: Structural characterization of the toluene-activated molybdenum complex [Cp∗Mo(CO)2(η3-CH2C6H5)]

R. Ramalakshmi (1, 2) , K. Maheswari (2) , D. Sharmila (2) , A. Paul (2) , T. Roisnel (1) , J.-F. Halet (1) , S. Ghosh (2)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 IIT Madras - Indian Institute of Technology Madras

Reactions of cyclopentadienyl transition-metal halide complexes [Cp*Mo(CO)Cl], 1, and [CpFe(CO)I], 2, (Cp = CH; Cp* = η-CMe) with borate ligands are reported. Treatment of 1 with [NaBt] (Bt = dihydrobis(2-mercapto-benzothiazolyl)borate) in toluene yielded [Cp*Mo(CO)(CHSN)], 3, and [Cp*Mo(CO)(η-CHCH)], 4, with a selective binding of toluene through C-H activation followed by orthometallation. Note that compound 4 is a structurally characterized toluene-activated molecule in which the metal is in η-coordination mode. Under similar reaction conditions, [NaPy] (Py = dihydrobis(2-mercaptopyridyl)borate) produced only the mercaptopyridyl molybdenum complex [Cp*Mo(CO)(CHSN)], 5, in good yield. On the other hand, when compound 2 was treated individually with [NaBt] (Bt = trihydro(2-mercapto-benzothiazolyl)borate) and [NaPy] in THF, formation of the η-coordinated complexes [CpFe(CO)(CHSN)], 6, and [CpFe(CO)(CHSN)], 7, was observed. The solid-state molecular structures of compounds 3, 4, 6, and 7 have been established by single-crystal X-ray crystallographic analyses.

Mots clés: X ray crystallography; Transition metals; Toluene; Cyclopentadienyls; Molybdenum complex; Orthometallation; Activation analysis; Chlorine compounds; Ligands; Metal halides; Molybdenum; Single crystals; Reaction conditions; Selective binding; Solid-state molecular structure; Structural characterization; X-ray crystallographic analysis; Molybdenum compounds

Domaines: Chimie

R. Ramalakshmi, K. Maheswari, D. Sharmila, A. Paul, T. Roisnel, et al.. Reactivity of cyclopentadienyl transition metal(II) complexes with borate ligands: Structural characterization of the toluene-activated molybdenum complex [Cp∗Mo(CO)2(η3-CH2C6H5)]. Dalton Transactions, 2016, 45 (41), pp.16317--16324. ⟨10.1039/c6dt02641a⟩. ⟨hal-01398030⟩