Half-Sandwich Iminophosphonamide Rhodium Complexes as Highly Efficient Catalysts for Dehydrogenation of Dimethylamine-Borane

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Abstract

The dehydrogenation of dimethylamine-borane (DMAB) catalyzed by the iminophosphonamide rhodium(III) complexes [Cp*RhCl{Ph2P(N–p-Tol)(NR)}] (Iа, R = p-Tol; Ib, R = Me) in situ formed fulvene [(η4-C5Me4CH2)Rh(NPN)] (IIa, IIb) and diene [(η4-C5Me5H)Rh(NPN)] (IIIa, IIIb) rhodium(I) derivatives is studied. Catalysts IIIa and IIIb turn out to be the most active and demonstrate a TOF activity of 110 (IIIа) and 540 h–1 (IIIb) at 40°С in toluene. The activity decreases significantly in more polar and coordinating THF. At the same time, the rate of DMAB dehydrogenation by complexes Iа and Ib is lower by 10–30 times, and fulvene complexes Iа and Ib are rapidly deactivated after the active initial period (<20% conversion). The kinetic studies show that the reaction has the first order with respect to the substrate and catalyst. The model 11В NMR experiments confirm that the reaction proceeds via the intermediate formation of a monomer Me2N=BH2, which rapidly dimerizes to (Me2N–BH2)2. The mechanism of DMAB dehydrogenation with the formation of unstable hydride intermediate [Cp*RhH{Ph2P(N–p-Tol)(NR)}] (IVa, IVb) is proposed on the basis of the preliminarily 31Р NMR results and published data.

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About the authors

R. I. Nekrasov

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: nataliabelk@ineos.ac.ru
Russian Federation, Moscow

T. A. Peganova

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: nataliabelk@ineos.ac.ru
Russian Federation, Moscow

A. M. Kal´sin

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: nataliabelk@ineos.ac.ru
Russian Federation, Moscow

N. V. Belkova

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Author for correspondence.
Email: nataliabelk@ineos.ac.ru
Russian Federation, Moscow

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Supplementary files

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2. Scheme 1. Synthesis of complexes IIa, IIb and IIIa, IIIb.

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3. Scheme 2. The proposed isomerization of IIIa in IVa under the action of DMAB, accompanied by the transfer of a hydrogen atom from Cp*H to the Rh atom and the release of H2.

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4. Fig. 1. Dehydrogenation of DMAB catalyzed by complexes IIIa, IIIb in toluene and THF. Conditions: T = 40°C, [Rh] = 5.8 mM, [DMAB] = 0.145 M, Vp-ra = 2.1 ml.

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5. Fig. 2. Dehydrogenation of DMAB catalyzed by complexes Ia, Ib and IIa, IIb in toluene, in comparison with IIIa, IIIb. Conditions: T = 40°C, [Rh] = 2.9 mM, [DMAB] = 0.145 M, Vp-ra = 2.1 ml.

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6. Fig. 3. Dehydrogenation of DMAB (0.145 M) catalyzed by complex IIIb at 40 °C in toluene, depending on the concentration of the catalyst: first-order kinetic curves (left) and the dependence of knabl on [Rh].

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7. Fig. 4. Kinetics of dehydrogenation of DMAB (0.085 M, δB = 13 m.d.) catalyzed by complex IIIa (0.008 M) at 18 ° C in toluene-d8. Changes in the NMR spectrum of the 11V mixture.

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8. Fig. 5. Graphs of changes in the relative concentrations of boron-containing reaction products (left) and a first-order kinetic curve with calculation of the observed reaction rate constant (right). The conditions are as shown in Fig. 4.

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