Stabilizing P≡P: P22–, P2⋅–, and P20 as bridging ligands

Sun, Jian; Verplancke, Hendrik; Schweizer, Julia I.; Diefenbach, Martin; Würtele, Christian; Otte, Matthias; Tkach, Igor; Herwig, Christian; Limberg, Christian; Demeshko, Serhiy; Holthausen, Max C.; Schneider, Sven

doi:10.1016/j.chempr.2021.06.006

Cited by 23 publications

(13 citation statements)

References 85 publications

(86 reference statements)

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“…In most of these cases P 2 acts as a ligand bridging two metal centres in an η 2 ‐mode. Only very recently, triply bonded P≡P was stabilised in the coordination sphere of a platinum complex [5] . Upon heating white phosphorus above 1000 K, dissociation into diphosphorus occurs [6,7] .…”

Section: Introductionmentioning

confidence: 99%

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Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

Hierlmeier

Wolf

2022

Eur J Inorg Chem

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The generation of diphosphorus molecules P 2 under mild conditions in solution is a useful strategy to generate diphosphines via [4 + 2] cycloadditions. We recently described the release of P 2 units from the nickel butterfly complex [{(IMes)Ni(CO)} 2 (μ 2 ,η 2 :η 2 -P 2 )](IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) upon addition of CO gas. Herein, we developed an alternative protocol for the same process using heterocumulenes. In addition to formation of P 4 (the dimerisation product of P 2 ), the reactions afford nickel com-plexes of novel pincer-type ligands. Aryl isothiocyanates undergo a trimerisation within the coordination sphere of nickel and afford square planar nickel complexes with SÀ CÀ S pincer-ligand frameworks. Carbon disulfide coordinates to the [(IMes)Ni]fragment in an η 2 -fashion, affording a dinuclear complex. Similar products are formed when the N-heterocyclic carbene nickel(0) complex [(IMes)Ni(vtms) 2 ] is used as a precursor (vtms = vinyltrimethylsilane).

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Section: Introductionmentioning

confidence: 99%

“…Only very recently, triply bonded P�P was stabilised in the coordination sphere of a platinum complex. [5] Upon heating white phosphorus above 1000 K, dissociation into diphosphorus occurs. [6,7] However, the conditions of this gas-phase reaction render further reactions with P 2 difficult.…”

Section: Introductionmentioning

confidence: 99%

Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

Hierlmeier

Wolf

2022

Eur J Inorg Chem

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“…Multiple synthetic routes have been established for the formation of multinuclear diphosphorus complexes (24)(25)(26)(27). Most common among these is the reductive cleavage of the tetrahedral P 4 molecule (i.e., white phosphorus) by low-valent transition metal complexes or the photolytic fragmentation of P 4 in the presence of metal-based acceptor compounds (24,25).…”

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Side-on coordination of diphosphorus to a mononuclear iron center

Wang

Sears

Moore

et al. 2022

Science

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The diagonal relationship in the periodic table between phosphorus and carbon has set an expectation that the triple-bonded diatomic diphosphorus molecule (P 2 ) should more closely mimic the attributes of acetylene (HC≡CH) rather than its group 15 congener dinitrogen (N 2 ). Although acetylene has well-documented coordination chemistry with mononuclear transition metals, coordination complexes that feature P 2 bound to a single metal center have remained elusive. We report the isolation and x-ray crystallographic characterization of a mononuclear iron complex featuring P 2 coordination in a side-on, η 2 -binding mode. An analogous η 2 -bound bis-timethylsilylacetylene iron complex is reported for comparison. Nuclear magnetic resonance, infrared, and Mössbauer spectroscopic analysis—in conjunction with density functional theory calculations—demonstrate that η 2 -P 2 and η 2 -acetylene ligands exert a similar electronic demand on mononuclear iron centers but exhibit different reactivity profiles.

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“…9 Klapötke et al described with P3N21 the smallest structurally characterized discrete binary PN molecule so far. 10 The stabilization and activation of dipnictogens, e.g., N2, 11 P2, 12,13 and just recently PN 14 is still an ongoing endeavor in inorganic chemistry. Due to its high reactivity and the absence of a suitable molecular precursor for a mild release of PN, molecules containing embedded phosphorus mononitride units have been synthesized and stabilized in various fashions, e.g., N-heterocyclic carbenes, 15 anthracene (APNA), 16 or cyclo-tetraphosphazene.…”

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confidence: 99%

Taming Phosphorus Mononitride (PN)

Eckhardt

Riu

et al. 2021

Preprint

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Phosphorus mononitride (PN) only has a fleeting existence on Earth and molecular precursors for a mild release of the molecule to enable chemical synthesis in solution do not exist. Here we report the synthesis of an anthracene (A) based molecular precursor (N3PA) that dissociates into dinitrogen (N2), A and PN in solution with a first order half-life of roughly t 1/2 = 30 min at room temperature associated with an activation enthalpy of ΔH ⧧ = 19.5 ± 1.7 kcal mol –1 and an activation entropy of ΔS ⧧ = −8.8 ± 0.8 cal mol –1 K –1 . Heated under vacuum N3PA decomposes in an explosive fashion at around 42 °C as demonstrated in a molecular beam mass spectrometry (MBMS) study. N3PA serves as a PN transfer reagent as demonstrated in the synthesis of [(dppe)Fe(Cp*)(NP)][BArF24]. Surprisingly, the terminal N-bonded linkage isomer is energetically preferred due to significant covalent iron pnictogen bond character and associated less unfavorable Pauli repulsion in the metal-ligand interaction.

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Stabilizing P≡P: P22–, P2⋅–, and P20 as bridging ligands

Cited by 23 publications

References 85 publications

Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

Side-on coordination of diphosphorus to a mononuclear iron center

Taming Phosphorus Mononitride (PN)

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