Synthesis and characterisation of transition metal omplexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine

Durran, Sean E., Elsegood, Mark R.J., Noble, Thomas A., Smith, Martin B., Gelbrich, Thomas, Hursthouse, Michael and Light, Mark (2021) Synthesis and characterisation of transition metal omplexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine. European Journal of Inorganic Chemistry, 2021 (23), 2274-2280. (doi:10.1002/ejic.202100236).

Abstract

The one-step synthesis (44 % isolated yield) of the 1,5-benzodiazapine functionalised phosphine 1, C ₃₁H ₃₁N ₂OP, is reported. Bridge cleavage of {MCl(μ-Cl)(η ⁵-Cp*)} ₂ (M=Ir, Rh) with 2 equiv. of 1 in CH ₂Cl ₂ gave the mononuclear compounds [MCl ₂(η ⁵-Cp*)(P-1)] (M=Ir, 2 a; M=Rh, 2 b) in which 1 functions as a P-monodentate ligand. Rapid C(sp ³)−H bond activation, at room temperature, is observed for 2 a leading to the unusual cyclometallated complex [Ir(η ⁵-Cp*)(P,N,C-1)]Cl ₂ 3 (or 3‘) bearing an anionic P/N _amine/C-terdentate ligand. Reaction of [Pt(CH ₃)Cl(η ⁴-cod)] with one equiv. of 1 led to [Pt(CH ₃)Cl(P,N-1)] 4, suggesting that 3 may form via an intermediate Ir ^III cationic species in which the ligand is P,N-bound. The Ir ^I complex [IrCl(η ⁴-cod)(P-1)] 5 does not, under similar conditions, show any evidence for C−H activation. Single crystal X-ray studies on 1, 2 a, 2 b, 3, 3‘, 4, and 5 reveal intramolecular N ⋅⋅⋅ H−O H-bonding in all cases.

This record has no associated files available for download.

Contributors

Author: Mark Light

Download statistics