Diamidophosphine as a Precursor of the Iminophosphonamidinate Ligand in the Yttrium Complex

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Abstract

Diamidophosphine tBuP(NHMes)2(H2L) is synthesized by the treatment of tBuPCl2 with two equivalents of KNHMes (Mes = 2,4,6-Me3C6H2). The reaction of H2L with potassium hydride in THF (THF is tetrahydrofuran) affords the anionic form HL− with the hydrogen atom migrating from nitrogen to phosphorus, which is confirmed by the 1H and 31P NMR data. The structure of the formed iminophosphonamidinate anion HL− is determined by X-ray diffraction (XRD) in the crystalline phase of K[K(THF)2](tBuPH(NMes)2)2 · C7H8 (KHL). The reaction of KHL with yttrium chloride gives complex [Y(tBuPH(NMes)2)2Cl] ([Y(HL)2Cl]) in which, according to the XRD data, ligands HL− are in the iminophosphonamidinate PH form. The 1H and 31P NMR spectra confirm that this structure of the complex exists in the solution.

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About the authors

A. Yu. Konokhova

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: konch@niic.nsc.ru
Russian Federation, Novosibirsk

M. Yu. Afonin

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: konch@niic.nsc.ru
Russian Federation, Novosibirsk

T. S. Sukhikh

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: konch@niic.nsc.ru
Russian Federation, Novosibirsk

S. N. Konchenko

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Author for correspondence.
Email: konch@niic.nsc.ru
Russian Federation, Novosibirsk

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Supplementary files

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2. Scheme 1. Anionic ligands and their protonated forms (proligands) appearing in this work. In all cases, Ri are different or identical aliphatic, aromatic, or heterocyclic radicals.

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3. Scheme 2. Synthesis of diamidophosphine H2L, its deprotonation with potassium hydride and synthesis of the [Y(HL)2Cl] complex.

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4. Fig. 1. Structure of K[K(THF)2](tBuPH(NMes)2)2 × C7H8 (KHL): packing of chains of alternating HL anions and potassium cations in a crystal (a); structure of the structural block K[K(THF)2](tBuPH(NMes)2)2 (b). CH3 groups of mesityl fragments and hydrogen atoms at carbon atoms are not shown. The contacts of potassium ions with nitrogen atoms and the π system of aromatic cycles are shown in dotted lines.

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5. Fig. 2. The structure of the molecule [Y(tBuPH(NMes)2)2Cl]([Y(HL)2Cl]). The CH3 groups of mesitylene fragments and hydrogen atoms at carbon atoms are not shown.

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