Transformation of white phosphorus in the coordination sphere of nickel complexes with σ-donating ligands

Budnikova, Yu. G.; Kafiyatullina, A. G.; Balueva, A. S.; Kuznetsov, Roman M.; Морозов, В. И.; Sinyashin, Оleg G.

doi:10.1023/b:rucb.0000012364.31262.ca

Cited by 7 publications

(3 citation statements)

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“…Their structures were determined by NMR and ESR spectroscopies, elemental analysis, and cyclic voltammetry. 12 The cyclic voltammograms of complexes 1 and 2 show reversible reduction corresponding to the Ni I /Ni 0 redox transition (see Fig. 4…”

Section: Methodsmentioning

confidence: 99%

“…11 Bis[1,1,1 tris(diphenylphosphinomethyl)ethane]phos phiridinonickel(II) bistetrafluoroborate [Ni 2 P 3 (triphos) 2 ](BF 4 ) 2 and 1,1´,5,5´ bis[methylenedi(p phenylene)]di(3,7 diphenyl 1,5 diaza 3,7 diphosphacyclooctane)phosphiridinonickel(II) bistetrafluoroborate [Ni 2 P 3 (n 2 p 2 )](BF 4 ) 2 were synthesized by a previously described procedure. 12 The data of 31 P NMR spectroscopy of 5•10 -2 M solutions of Ni(BF 4 ) 2 L in DMF in the presence of white phosphorus are presented in Table 1. The complexes NiX 2 L were synthesized by the mixing of equivalent amounts of a nickel salt and the corresponding ligand in hot ethanol followed by the filtration of the complex and drying in vacuo for a day.…”

Section: Methodsmentioning

confidence: 99%

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Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

et al. 2005

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Routes of white phosphorus activation in the coordination sphere of the nickel complexes with different ligands are shown. The first route is based on the coordination of a P 4 molecule with the metal, resulting in the deformation of the P 4 tetrahedron without destruction. This case is characteristic of the NiX 2 L complexes, which are reduced at higher cathodic potentials (|E red | > 0.9 V) (X = BF 4 , Br, and Cl; L is bpy in DMF, MeCN, and acetone; 2,9 dimethyl 1,10 phenanthroline (phen) and PPh 3 in DMF and acetone). To cleave the P-P bonds in the P 4 molecule, this complex should be reduced on the electrode. The second route is the oxidation of white phosphorus in the coordination sphere of the Ni II complex. It occurs when the complex has a sufficiently high oxidizing ability and is reduced rather easily (|E red | < 0.9 V) (X = BF 4 , L is 1,1,1 tris(diphenylphosphinomethyl)ethane (triphos) in acetone; 1,1´,5,5´ bis[methylenedi(p phenylene)]di(3,7 diphenyl 1,5 diaza 3,7 diphosphacyclooctane) (n 2 p 2 ) in DMF; phen and PPh 3 in MeCN). The P 4 molecule opening is observed to form a new Ni I complex containing the (P 3 ) fragment, for example, [(triphos)Ni(P 3 )Ni(triphos)](BF 4 ) 2 .The electrochemical activation of reagents in processes involving organometallic compounds is very efficient. 1-4 This approach combines advantages of catalysis by metal complexes and activation by means of electrochemical electron transfer. The activation of white phosphorus is a practically important task because of the necessity to search for new routes of direct syntheses of organophos phorus compounds. Numerous reactions of P 4 tetrahedron transformation were described, which resulted in various polyphosphorus structures among which metal complexes with cyclic P 3 , P 5 , and P 6 ligands, 4 as well as the P 4 ligand, 5,6 seem to be most interesting. The P 4 molecule is activated due to the deformation of the P 4 tetrahedron and, as a consequence, the P-P bond length changes. In ultimate cases, these bonds can cleave to form new polyphosphorus structures. Until now, P 4 transformation was studied only by NMR spectroscopy, and very stable compounds were examined. Evidently, the more stable these structures, the more difficult is the preparation of related basis organophosphorus compounds, i.e., the main task of the elemental phosphorus chemistry is the direct transformation of phosphorus into organophosphorus compounds (OPC), excluding traditional steps of its chlo rination. At the same time, metal complexes with poly phosphorus ligands can possess a set of useful properties: semiconductivity, corrosion resistance, and others 7 and act as stable intermediates in various reactions, which are of independent interest.In this work, we attempted to estimate the reactivity of several nickel complexes with σ donor ligands toward white phosphorus using cyclic voltammetry (CV), pre parative electrolysis, and 31 P NMR spectroscopy. The nickel complexes were chosen, because they are catalysts of some reactions of white phosphorus functio...

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

et al. 2005

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“…This indicates that 1 H -triphosphirene ( c -HP 3 , 3 ) should be easier to prepare than its isovalent 1 H -triazirine ( c -HN 3 , 2 ) counterpart. However, although white phosphorus (P 4 ) can be transformed into the cyclo -P 3 ligand in the process of generating nickel(II) complexes, , the preparation of 1 H -triphosphirene ( c -HP 3 , 3 ) has remained a fundamental synthetic challenge due to the lack of preparative synthetic chemistry routes to isolate the cyclo -P 3 as σ-donor ligand. Consequently, 1 H -triphosphirene ( c -HP 3 , 3 ) along with its acyclic 2-triphosphenylidene (HP 3 , 4 ) isomer exemplifies one of the least explored classes of inorganic molecules.…”

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Detection of 1H-Triphosphirene (c-HP₃) and 2-Triphosphenylidene (HP₃): The Isovalent Counterparts of 1H-Triazirine (c-HN₃) and Hydrazoic Acid (HN₃)

Zhang

Zhu

Eckhardt

et al. 2022

J. Phys. Chem. Lett.

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The hitherto elusive 1H-triphosphirene (c-HP3) and 2-triphosphenylidene (HP3) molecules were prepared in low-temperature matrices and detected isomer selectively through photoionization coupled with reflectron time-of-flight mass spectrometry (PI-ReTOF-MS). Our results reveal a thermodynamically preferred cyclic isomer (c-HP3) compared to the acyclic structure (HP3) in contrast to the isovalent HN3 system favoring hydrazoic acid (HN3) compared to 1H-triazirine (c-HN3). Theoretical computations suggest a ring strain energy of 1H-triphosphirene (c-HP3) of only 35 kJ mol–1, which is significantly lower than the tetrahedral phosphorus molecule (P4) of 74 kJ mol–1. This work provides a fundamental benchmark to understand the electronic structure and chemical bonding of cyclic molecules and offers an unconventional approach to preparing highly strained, still elusive molecules such as 1H-triazirine and tetrahedral tetranitrogen (N4) in the near future involving progressive nonequilibrium chemistries.

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Nickel complexes with cyclic ligands containing P and N atoms as coordination sites: novel biomimetic catalysts for hydrogen oxidation

et al. 2013

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Transformation of white phosphorus in the coordination sphere of nickel complexes with σ-donating ligands

Cited by 7 publications

References 8 publications

Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

Detection of 1H-Triphosphirene (c-HP₃) and 2-Triphosphenylidene (HP₃): The Isovalent Counterparts of 1H-Triazirine (c-HN₃) and Hydrazoic Acid (HN₃)

Nickel complexes with cyclic ligands containing P and N atoms as coordination sites: novel biomimetic catalysts for hydrogen oxidation

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Transformation of white phosphorus in the coordination sphere of nickel complexes with σ-donating ligands

Cited by 7 publications

References 8 publications

Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

Detection of 1H-Triphosphirene (c-HP3) and 2-Triphosphenylidene (HP3): The Isovalent Counterparts of 1H-Triazirine (c-HN3) and Hydrazoic Acid (HN3)

Nickel complexes with cyclic ligands containing P and N atoms as coordination sites: novel biomimetic catalysts for hydrogen oxidation

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Detection of 1H-Triphosphirene (c-HP₃) and 2-Triphosphenylidene (HP₃): The Isovalent Counterparts of 1H-Triazirine (c-HN₃) and Hydrazoic Acid (HN₃)