π-Komplexe

Perkampus, H.‐H.

doi:10.1007/978-3-642-48186-4_4

Cited by 3 publications

(2 citation statements)

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“…However, a closer look at the Sb···C aryl,PNP distances revealed a weak cation–anion interaction, as manifested by a shortened Sb···C aryl,PNP distance [ d (Sb1···C58) = 3.677(4) Å, compared to ∑ r van der Waals = 3.76 Å], which can be understood as a weak Menshutkin-type interaction (Figure ). − …”

Section: Resultsmentioning

confidence: 99%

Heavy Neutral and Anionic Pnictogen Thiocyanates

et al. 2019

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When [PPN]SCN (1; PPN = [Ph3P–N–PPh3]) is treated with Me3Si–SCN in methanol, [PPN][H(NCS)2] (2), a hydrogen diisothiocyanate salt bearing the [H(NCS)2]− anion, was generated, isolated, and fully characterized. Pure heavy E(NCS)3 [E = Sb (3), Bi (4)] species were obtained from the reaction of EF3 and an excess of Me3Si–SCN, while the tetrahydrofuran (THF) solvates E(NCS)3·THF were isolated when the product was recrystallized from THF. When 2 equiv of 1 was combined with Me3Si–SCN and SbF3, [PPN]2[Sb(NCS)5] (5) could be isolated. When 1 was added to BiF3, [PPN]2[Bi(NCS)3(SCN)2·THF] (6·THF), containing three SCN– ions coordinating via the N atom and two coordinating via the S atom, was isolated after recrystallization from THF. The structures of 1, 2, 3·THF, 4·THF, 5, and 6·THF were determined. 3·THF displayed a typical [3 + 3] coordination mode with a trigonal-pyramidal environment in the first coordination sphere of the Sb3+ ion, and the dianion of 5, [Sb(NCS)5]2–, featured a classical square-pyramidal molecular geometry around the Sb3+ ion with one additional Menshutkin-type interaction to one aryl ring of the [PPN]+ cation. 4·THF exhibited a distorted pentagonal-bipyramidal structure within a two-dimensional network, while in 6·THF, an octahedrally surrounded Bi3+ ion was observed.

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Section: Resultsmentioning

confidence: 99%

Heavy Neutral and Anionic Pnictogen Thiocyanates

et al. 2019

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“…While each nitrogen adopts a trigonal-pyramidal structure, the coordination environment around each bismuth is best described as distorted pseudotrigonal bipyramidal, with the lone pair occupying the equatorial position. A closer look at the structure reveals Menshutkin-type interactions ,− for each bismuth center, each with one benzene molecule in an η 6 fashion [Figure ; Bi–C distances between 3.35 and 3.57 Å; cf. ∑ r VdW (C–Bi) = 3.77 Å] .…”

Section: Structure and Bondingmentioning

confidence: 99%

Synthesis and Structure of Bismuth–Nitrogen Cage Compounds and Heterocubanes: [Cl-Bi(μ₃-N-TMP)]₄: A Dimer of a 1,3-Dichloro-cyclo-dibismadiazane

2020

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The reaction of TMP-NH 2 [TMP = m,m-(CF 3 ) 2 -C 6 H 3 ] with 2 equiv of n-BuLi led to the in situ formation of Li 2 [N-TMP], which, after the addition of BiCl 3 , formed a [Cl-Bi(μ 3 -N-TMP)] 4 -type heterocubane in up to 30% yield. Transmetalation reactions, thought of as alternatives, starting from the analogous tin−nitrogen heterocubane [Sn(μ 3 -N-TMP)] 4 and BiCl 3 resulted in the isolation of a complex reaction mixture from which different Bi−N and Bi−Sn−N cage compounds could be isolated. The structures of all cage compounds that contain bismuth are discussed, and the thermodynamics of the formation of [Cl-Bi(μ 3 -N-TMP)] 4 are highlighted. In an attempt to isolate Li 2 [N-TMP], generated in situ from TMP-NH 2 and 2 equiv of n-BuLi, it was possible to isolate a lithium salt with a negatively charged lithium cluster of the type [Li 9 (N-TMP) 5 F] 2− with an unusual Li 9 N 5 F skeleton.

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A Bismuth–Arene σ‐Complex – On the Edge of Menshutkin‐Type Complexes

et al. 2019

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Mes*N(SiMe 3 )BiCl 2 (1, Mes* = 2,4,6-tri-tert-butylphenyl) can be referred to as a hidden iminobismuthane, Mes*N=BiCl, which was thought to be generated in-situ upon Me 3 SiCl elimination triggered by a Lewis acid such as GaCl 3 . Therefore, the reactivity of aminobismuthane 1 was studied to find a synthesis route for the formation of a tetrazabismuthole in a [3+2] cycloaddition reaction with a covalently bound azide. However, reaction of 1 with GaCl 3 cleanly led to [Mes*N(SiMe 3 )-BiCl][GaCl 4 ] (2[GaCl 4 ]), a compound with a Bi-arene σ-complex. Utilizing Ag[WCA] salts (WCA = weakly coordinating anion) for [a]

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π-Komplexe

Cited by 3 publications

References 149 publications

Heavy Neutral and Anionic Pnictogen Thiocyanates

Heavy Neutral and Anionic Pnictogen Thiocyanates

Synthesis and Structure of Bismuth–Nitrogen Cage Compounds and Heterocubanes: [Cl-Bi(μ₃-N-TMP)]₄: A Dimer of a 1,3-Dichloro-cyclo-dibismadiazane

A Bismuth–Arene σ‐Complex – On the Edge of Menshutkin‐Type Complexes

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π-Komplexe

Cited by 3 publications

References 149 publications

Heavy Neutral and Anionic Pnictogen Thiocyanates

Heavy Neutral and Anionic Pnictogen Thiocyanates

Synthesis and Structure of Bismuth–Nitrogen Cage Compounds and Heterocubanes: [Cl-Bi(μ3-N-TMP)]4: A Dimer of a 1,3-Dichloro-cyclo-dibismadiazane

A Bismuth–Arene σ‐Complex – On the Edge of Menshutkin‐Type Complexes

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Synthesis and Structure of Bismuth–Nitrogen Cage Compounds and Heterocubanes: [Cl-Bi(μ₃-N-TMP)]₄: A Dimer of a 1,3-Dichloro-cyclo-dibismadiazane