128388-72-7

Upstream product

• 133579-10-9 2,2-di-tert-butyl-1,1-bis(diisopropylamino)diphosphane 
• 56183-63-2 bis(diisopropylamino)chlorophosphine 
• 81476-73-5 (cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride 
• 153295-13-7 C₂₄H₃₈N₂P₂ 
• 65567-06-8 lithium diphenylphosphide 
• 20684-97-3 chloro(diisopropylamino)(phenyl)phosphine 

Downstream Products

• 68880-43-3 C₁₂H₂₈N₂P⁽¹⁺⁾ 

Relevant academic research and scientific papers

Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl, and amino substituents

We present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via a salt metathesis reaction of halophosphanes with metal phosphides in high yield. We vastly expanded this group of compounds by obtaining the first mono- A nd tri-amino-substituted systems. The structures of the isolated compounds were characterized by NMR spectroscopy and X-ray diffraction. The isolated unsymmetrical diphosphanes have no tendency to rearrange to the corresponding symmetrical species. Additionally, we proposed the general classification of diphosphanes based on the number of different groups attached to phosphorus atoms and their distribution within a molecule. To investigate the impact of substituents on the properties of P-centers and a molecule as a whole, we conducted a DFT study on the electronic and steric properties of the obtained systems. The experimental and theoretical results can be very useful for designing P-P systems with desired properties.

Synthetic, Structural, and Spectroscopic Characterization of a Novel Family of High-Spin Iron(II) [(β-Diketiminate)(phosphanylphosphido)] Complexes

This work describes a series of iron(II) phosphanylphosphido complexes. These compounds were obtained by reacting lithiated diphosphanes R2PP(SiMe3)Li (R = t-Bu, i-Pr) with an iron(II) β-diketiminate complex, [LFe(μ2-Cl)2Li(DME)2] (1), where DME = 1,2-dimethoxyethane and L = Dippnacnac (β-diketiminate). While the reaction of 1 with t-Bu2PP(SiMe3)Li yields [LFe(η1-Me3SiPP-t-Bu2)] (2), that of 1 with equimolar amounts of i-Pr2PP(SiMe3)Li, in DME, leads to [LFe(η2-i-Pr2PPSiMe3)] (3). In contrast, the reaction of 1 with (i-Pr2N)2PP(SiMe3)Li provides not an iron-containing complex but 1-[(diisopropylamino)phosphine]-2,4-bis(diisopropylamino)-3-(trimethylsilyl)tetraphosphetane (4). The structures of 2-4 were determined using diffractometry. Thus, 2 exhibits a three-coordinate iron site and 3 a four-coordinate iron site. The increase in the coordination number is induced by the change from an anticlinal to a synclinal conformation of the phoshpanylphosphido ligands. The electronic structures of 2 and 3 were assessed through a combined field-dependent 57Fe M?ssbauer and high-frequency and -field electron paramagnetic resonance spectroscopic investigation in conjunction with analysis of their magnetic susceptibility and magnetization data. These studies revealed two high-spin iron(II) sites with S = 2 ground states that have different properties. While 2 exhibits a zero-field splitting described by a positive D parameter (D = +17.4 cm-1 E/D = 0.11) for 3, this parameter is negative [D = ?25(5) cm-1 E/D = 0.15(5)]. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations provide insights into the origin of these differences and allow us to rationalize the fine and hyperfine structure parameters of 2 and 3. Thus, for 2, the spin-orbit coupling mixes a z2-type ground state with two low-lying {xz/yz} orbital states. These interactions lead to an easy plane of magnetization, which is essentially parallel to the plane defined by the N-Fe-N atoms. For 3, we find a yz-type ground state that is strongly mixed with a low-lying z2-type orbital state. In this case, the spin-orbit interaction leads to a partial unquenching of the orbital momentum along the x axis, that is, to an easy axis of magnetization oriented roughly along the Fe-P bond of the phosphido moiety.

Formation of polyphosphorus ligands mediated by zirconium and hafnium complexes

The reactions of R2P-P(SiMe3)Li (R = tBu, iPr, iPr2N) with [Cp2MCl 2] (M = Zr, Hf), [Cp*z.ast;CpZrCl2] and [CpZrCl 3] yielded polyphosphorus (mainly hexaphosphorus) compounds which can be viewed as intermediates between R2P-P(SiMe3)Li and derivatives of 1,2,3,4-tetraphosphabicyclo[1.1.0] butane. Thus R 2P-P(SiMe3)Li can act as a building block for the formation of the P2 ligand and the R2P-P(P2) and R2P-P(P2)P-PR2 moieties. Solid state structures of zirconium(IV) and hafnium(IV) complexes with R2P- P(P2) and R2P-P(P2)P-PR2 ligands were established by X-ray studies.

Redox Properties of Diphosphanes

Diphosphanes undergo electrochemical one-electron oxidation.In case amino groups are at the phosphorus, the resulting distonic diphosphane radical cations disproportionate readily into a dication and a diphosphane; the former separates into two phosphenium cations. Key Words: Diphosphanes / Cyclic voltammetry / Calculations, MNDO, ab initio