Synthesis of a 1-aza-2-phospha-acenaphthene complex profiting from coordination enabled chloromethane elimination

Biskup, David; Bergmann, Tom; Schnakenburg, Gregor; Gomila, Rosa M.; Frontera, Antonio; Streubel, Rainer

doi:10.1039/d3ra04352e

Cited by 1 publication

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References 39 publications

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“…Species I (Figure 1) with two differing Group 15 peri-atoms display intriguing dative bonding and NMR properties [16,17]. Surprisingly, only two bis(tertiary) phosphine-stibine and phosphine-bismuthine peri-substituted species have been reported to date: I Sb [18] and I Bi [19].…”

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

View full text Add to dashboard Cite

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Synthesis of a 1-aza-2-phospha-acenaphthene complex profiting from coordination enabled chloromethane elimination

Abstract: The formation of an annulated P-heterocycle is described using a bond activation elimination sequence through intramolecular N→P interactions in peri-substituted naphthalene derivatives and through transition metal coordination.

Cited by 1 publication

References 39 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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