351884-56-5Relevant academic research and scientific papers
Ruthenium p-Cymene Iminophosphonamide Complexes: Activation under Basic Conditions and Transfer Hydrogenation Catalysis
Sinopalnikova, Iana S.,Peganova, Tatyana A.,Belkova, Natalia V.,Deydier, Eric,Daran, Jean-Claude,Shubina, Elena S.,Kalsin, Alexander M.,Poli, Rinaldo
, p. 2285 - 2299 (2018)
Complex [(η6-Cym)RuCl(NPN)] {Cym = p-cymene; NPN = (pTolN)2PPh2} (1) yields a thermally sensitive hydride derivative [(η6-Cym)RuH(NPN)] (2) by reaction with iPrOH in the presence of a strong base, via an observable isopropoxide intermediate [(η6-Cym)Ru(OiPr)(NPN)] (3), or with NaBHEt3 in toluene. Partial conversion also occurs in iPrOH in the absence of base. 2 is stabilized by dihydrogen bonding with isopropyl alcohol, but attempts to isolate it induce isomerization by hydride migration to a ring CH position to yield a 16-electron cyclohexadienyl derivative [{η5-p-C6H5(Me)(iPr)}Ru(NPN)], which has been crystallographically characterized as a disordered mixture of two regioisomers (4/4′). Complex 2 is able to release H2 upon treatment with medium strength proton donors (fluorinated alcohols), but also slowly with iPrOH. 2 is an active catalyst for the transfer hydrogenation of acetophenone to phenylethanol in isopropyl alcohol. The catalytic transformation is first order in acetophenone and first order in catalyst, with k = 117 ± 10 m–1 h–1 at 40 °C. The temperature dependence of the rate constant (25–80 °C) gave the activation parameters ΔH? = 9.6 ± 1.3 kcal mol–1 and ΔS? = –31 ± 4 cal mol–1 K–1. DFT calculations have validated the slow isomerization of 2 to 4/4′ (high energy TS), the preference of the cyclohexadienyl system for 4/4′ relative to the other isomers 4Me and 4iPr, where the hydride has migrated to the CMe or CiPr position, and suggest that the hydrogen transfer mechanism involves outer sphere hydride transfer to the ketone substrate with H-bonding assistance of isopropyl alcohol to yield a σ complex intermediate [(η6-Cym)Ru+(NPN){H-C(Me)(Ph)O–}].
The half-sandwich 18- and 16-electron arene ruthenium iminophosphonamide complexes
Peganova, Tat'Yana A.,Sinopalnikova, Iana S.,Peregudov, Alexander S.,Fedyanin, Ivan V.,Demonceau, Albert,Ustynyuk, Nikolai A.,Kalsin, Alexander M.
, p. 17030 - 17041 (2016/11/09)
Novel half-sandwich 18ē and 16ē arene ruthenium iminophosphonamide complexes [(η6-C6Me6)RuCl{(R′N)2PR2}] (3a-c) and [(η6-C6Me6)Ru{(R′N)2PR2}]+(X-) (4a-c) (a, R = Ph, R′ = p-Tol; b, R = Et, R′ = p-Tol; c, R = Ph, R′ = Me. X = BF4, PF6 or BArF4) were synthesized. The elongated Ru-Cl bond in the 18ē complexes is shown to dissociate even in apolar solvents to form the corresponding 16ē cations, which can be readily isolated as salts with non-coordinating anions. The coordinatively unsaturated 16ē complexes are stable species due to efficient π-electron donation from the nitrogen atoms of the zwitterionic NPN-ligand. The ruthenium iminophosphonamides are moderately active in the ROMP polymerization of norbornene; the 16ē complexes 4a,b yield high molecular weight polymers (Mn ～ 300 × 103) with a narrow distribution Mw/Mn ～ 1.6, while the 18ē complexes 3a,b give polymers of lower molecular weight (Mn 3) with a wider polydispersity index Mw/Mn ～ 2.5.
