Comparing London dispersion pnictogen–π interactions in naphthyl-substituted dipnictanes

Gehlhaar, Alexander; Schiavo, Eduardo; Wölper, Christoph; Schulte, Yannick; Auer, Alexander A.; Schulz, Stephan

doi:10.1039/d2dt00477a

Cited by 5 publications

(2 citation statements)

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“…The related Sb−Sb bonded species F [12], as well as the doubly backboned species G [13][14][15] and H [11], have received significant attention recently, and a few transition metal complexes with these as ligands have also been reported [13].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Studies of peri-Substituted Acenaphthenes with Tertiary Phosphine and Stibine Groups

Taylor,

Lawson,

Cordes

et al. 2024

Molecules

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Two mixed peri-substituted phosphine-chlorostibines, Acenap(PiPr2)(SbPhCl) and Acenap(PiPr2)(SbCl2) (Acenap = acenaphthene-5,6-diyl) reacted cleanly with Grignard reagents or nBuLi to give the corresponding tertiary phosphine-stibines Acenap(PiPr2)(SbRR’) (R, R’ = Me, iPr, nBu, Ph). In addition, the Pt(II) complex of the tertiary phosphine-stibine Acenap(PiPr2)(SbPh2) as well as the Mo(0) complex of Acenap(PiPr2)(SbMePh) were synthesised and characterised. Two of the phosphine-stibines and the two metal complexes were characterised by single-crystal X-ray diffraction. The peri-substituted species act as bidentate ligands through both P and Sb atoms, forming rather short Sb-metal bonds. The tertiary phosphine-stibines display through-space J(CP) couplings between the phosphorus atom and carbon atoms bonded directly to the Sb atom of up to 40 Hz. The sequestration of the P and Sb lone pairs results in much smaller corresponding J(CP) being observed in the metal complexes. QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis employing Naturalised Orbitals for Chemical Valence) computational techniques were used to provide additional insight into a weak n(P)→σ*(Sb-C) intramolecular bonding interaction (pnictogen bond) in the phosphine-stibines.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Studies of peri-Substituted Acenaphthenes with Tertiary Phosphine and Stibine Groups

Taylor,

Lawson,

Cordes

et al. 2024

Molecules

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“…We recently reported on dipnictanes Pn 2 Naph 2 (Pn = As, Sb, Bi) 14 and bis(diphenylpnicta)naphthalenes (Ph 2 Pn) 2 Naph (Pn = Sb, Bi) 15 of the heaviest group 15 elements. Due to our general interest in pnictogen-centered radicals, 16 we investigated single electron transfer reactions of the latter.…”

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Bisstibane–distibane conversionviaconsecutive single-electron oxidation and reduction reaction

et al. 2022

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Improved syntheses of doubly naphthalene-bridged diphosphine and its diiminodiphosphorane derivatives linking two Cu(I) centers

et al. 2023

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Comparing London dispersion pnictogen–π interactions in naphthyl-substituted dipnictanes

Abstract: Using a combination of NMR, X-ray diffraction and quantum chemistry, the structure-directing role of London Dispersion (LD) is demonstrated for dibismuthane Bi2Naph2 (1). 1 shows intermolecular Bi···π contacts in the...

Cited by 5 publications

References 48 publications

Synthesis and Structural Studies of peri-Substituted Acenaphthenes with Tertiary Phosphine and Stibine Groups

Synthesis and Structural Studies of peri-Substituted Acenaphthenes with Tertiary Phosphine and Stibine Groups

Bisstibane–distibane conversionviaconsecutive single-electron oxidation and reduction reaction

Improved syntheses of doubly naphthalene-bridged diphosphine and its diiminodiphosphorane derivatives linking two Cu(I) centers

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