Bisstibane–distibane conversion<i>via</i>consecutive single-electron oxidation and reduction reaction

Gehlhaar, Alexander; Weinert, Hanns Micha; Wölper, Christoph; Semleit, Nina; Haberhauer, Gebhard; Schulz, Stephan

doi:10.1039/d2cc01986h

Cited by 1 publication

(2 citation statements)

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“…Prototypical naphthalene bis(stibines) with dimethylstibino (D1) and diphenylstibino groups (D2) were synthesised by Reid, together with their Mo(0) and Pt(II) complexes [10]. The aryl species D2 (both naphthalene and acenaphthene variants) and D3 (naphthalene variant) were recently structurally characterised by Schulz, together with the two bis(bismuthines) E [11,12]. However, no structural data for any of the bis(stibine) or bis(bismuthine) metal complexes have been published to date.…”

Section: Introductionmentioning

confidence: 99%

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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%

“…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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Bisstibane–distibane conversionviaconsecutive single-electron oxidation and reduction reaction

Abstract: Peri-substituted naphthalene complexes (Trip2Pn)2Naph (E = Sb 1, Bi 2) were synthesized and their redox behaviour investigated. Oxidation of 1 with [Fc][BArF] (BArF = B(C6F5)4) yielded [(Trip2Sb)(TripSb)Naph][BArF] (3) containing the...

Cited by 1 publication

References 65 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

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