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Kornev AN, Belina NV, Sushev VV, et al. The first structurally characterized metal (kappa(2)N,P)-phosphinohydrazides: the key to understanding the intramolecular rearrangement R2P-NR'-NR'-M --> R'N=PR2-NR'-M. Metalloderivatives of diisopropylphosphinohydrazines: synthesis and properties. Inorg Chem. 2009;48(12):5574-83doi: 10.1021/ic900135b.
Kornev, A. N., Belina, N. V., Sushev, V. V., Fukin, G. K., Baranov, E. V., Kurskiy, Y. A., Poddelskii, A. I., Abakumov, G. A., Lönnecke, P., & Hey-Hawkins, E. (2009). The first structurally characterized metal (kappa(2)N,P)-phosphinohydrazides: the key to understanding the intramolecular rearrangement R2P-NR'-NR'-M --> R'N=PR2-NR'-M. Metalloderivatives of diisopropylphosphinohydrazines: synthesis and properties. Inorganic chemistry, 48(12), 5574-83. https://doi.org/10.1021/ic900135b
Kornev, Alexander N, et al. "The first structurally characterized metal (kappa(2)N,P)-phosphinohydrazides: the key to understanding the intramolecular rearrangement R2P-NR'-NR'-M --> R'N=PR2-NR'-M. Metalloderivatives of diisopropylphosphinohydrazines: synthesis and properties." Inorganic chemistry vol. 48,12 (2009): 5574-83. doi: https://doi.org/10.1021/ic900135b
Kornev AN, Belina NV, Sushev VV, Fukin GK, Baranov EV, Kurskiy YA, Poddelskii AI, Abakumov GA, Lönnecke P, Hey-Hawkins E. The first structurally characterized metal (kappa(2)N,P)-phosphinohydrazides: the key to understanding the intramolecular rearrangement R2P-NR'-NR'-M --> R'N=PR2-NR'-M. Metalloderivatives of diisopropylphosphinohydrazines: synthesis and properties. Inorg Chem. 2009 Jun 15;48(12):5574-83. doi: 10.1021/ic900135b. PMID: 19438251.
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Inorg Chem. 2009 Jun 15;48(12):5574-83. doi: 10.1021/ic900135b.

The first structurally characterized metal (kappa(2)N,P)-phosphinohydrazides: the key to understanding the intramolecular rearrangement R2P-NR'-NR'-M --> R'N=PR2-NR'-M. Metalloderivatives of diisopropylphosphinohydrazines: synthesis and properties.

Inorganic chemistry

Alexander N Kornev, Natalia V Belina, Vyacheslav V Sushev, Georgy K Fukin, Evgenii V Baranov, Yuriy A Kurskiy, Andrei I Poddelskii, Gleb A Abakumov, Peter Lönnecke, Evamarie Hey-Hawkins

Affiliations

  1. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinin Street, 603950 Nizhny Novgorod, Russia. [email protected]

PMID: 19438251 DOI: 10.1021/ic900135b

Abstract

A number of novel phosphinohydrazines, iPr(2)P-NPh-NPh-H (1), iPr(2)P-NH-NH-PiPr(2) (2), iPr(2)P-NMe-NH-PiPr(2) (3), and H-NMe-NH-PiPr(2) (4), were prepared and characterized. The interaction of 1 with 1 equiv of n-BuLi afforded a complex compound [Li(DME)(3)][Li{(NPh-NPh-PiPr(2))-kappaN}(2)] (5). The reaction of 5 with NiBr(2) resulted in the formation of the first stable transition metal phosphinohydrazide [Ni{(NPh-NPh-PiPr(2))-kappa(2)N,P}(2)] (6). Similarly, the cobalt(II) derivative [Co{(NPh-NPh-PiPr(2))-kappa(2)N,P}(2)] (7) was prepared by the reaction of 1 with Co[N(SiMe(3))(2)](2). An X-ray study reveals formation of the complexes containing elongated N-N bonds (1.443(1), 1.466(2), and 1.470(2) A for 5, 6, and 7, respectively) as compared with the starting material 1 (1.407(1) A). Nickel phosphinohydrazide 6 has a square-planar cis configuration; the cobalt complex 7 possesses a square-planar centrosymmetric trans configuration. The half-sandwich nickel(II) complex [CpNi{(NPh-NPh-PiPr(2))-kappa(2)N,P}] (8) was prepared by prolonged heating of phosphinohydrazine 1 with NiCp(2) in toluene. The lithiation of 3 with n-BuLi resulted in the formation of an iminophosphoranate [LiN=PiPr(2)-NMe-PiPr(2)] (13) (in situ), which is the product of insertion of a PiPr(2) group into the nitrogen-nitrogen bond. The hydrolysis of 13 followed by the addition of CoCl(2) gave the phosphino-iminophosphoranato complex [CoCl(2){(HN=PiPr(2)-NMe-PiPr(2))-kappa(2)N,P}] (15) according to X-ray investigation. The phosphinohydrazine 3 reacted with FeX(2) in toluene to form adducts (1:1) [FeX(2){(PiPr(2)-NMe-NH-PiPr(2))-kappa(2)P,P'}] (X = Cl (9), Br (10)), while CoCl(2) gave the complex salt [{Co(PiPr(2)-NMe-NH-PiPr(2))-kappa(2)P,P'}(2)(mu-Cl)(3)][CoCl(3)(THF)] (11). A THF solution of complex 11 shows thermochromic behavior.

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