Elementorganisch substituierte Ammonium‐Salze. Die Kristallstrukturen von [HN(SnMe3)3]I, [H2N(SnMe3)2][SnMe3Cl2] und [N(AsMe3)2]Br

Hillwig, Ralf; Harms, Κ.; Dehnicke, Kurt; Müller, Ulrich

doi:10.1002/zaac.199762301107

Cited by 18 publications

(16 citation statements)

References 18 publications

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“…This pattern is consistent with the fact that the most positive σ-hole on tin is expected to occur at this position, as bromine is more electron-withdrawing than the other atoms bound to tin. Finally, the Sn···I interactions present in crystals of tris(trimethylstannyl)ammonium iodide (refcode RONDAZ) [125] provide a nice example of chargeassisted TB. The existence of this type of TB further highlights the similarities of the different subsets of σ-hole interactions, as charge-assisted XBs [126] and charge-assisted PBs [31] have already been observed.…”

Section: Halogen Atoms As Tetrel Bond Acceptorsmentioning

confidence: 99%

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

et al. 2018

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Modeling indicates the presence of a region of low electronic density (a Bσ-hole^) on group 14 elements, and this offers an explanation for the ability of these elements to act as electrophilic sites and to form attractive interactions with nucleophiles. While many papers have described theoretical investigations of interactions involving carbon and silicon, such investigations of the heavier group 14 elements are relatively scarce. The purpose of this review is to rectify, to some extent, the current lack of experimental data on interactions formed by germanium and tin with nucleophiles. A survey of crystal structures in the Cambridge Structural Database is reported. This survey reveals that close contacts between Ge or Sn and lone-pair-possessing atoms are quite common, they can be either intra-or intermolecular contacts, and they are usually oriented along the extension of the covalent bond formed by the tetrel with the most electron-withdrawing substituent. Several examples are discussed in which germanium and tin atoms bear four carbon residues or in which halogen, oxygen, sulfur, or nitrogen substituents replace one, two, or three of those carbon residues. These close contacts are assumed to be the result of attractive interactions between the involved atoms and afford experimental evidence of the ability of germanium and tin to act as electrophilic sites, namely tetrel bond (TB) donors. This ability can govern the conformations and the packing of organic derivatives in the solid state. TBs can therefore be considered a promising and robust tool for crystal engineering.

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Section: Halogen Atoms As Tetrel Bond Acceptorsmentioning

confidence: 99%

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

et al. 2018

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“…(Ausnahme: Der terminal an ein Cu-Atom gebundene (NHMes) ± -Ligand in 7.) ± Imidoliganden (NR) 2± : (NMes) 2± (6); (NPh) 2± (9,10) ko È nnen l 3 -oder l 4 -Bru È ckenfunktion zwischen Cu-Atomen einnehmen.…”

Section: Die Moleku è Lstruktur Von [Pph 3 (C 6 H 4 )Cunhmes] (7) Im unclassified

Neue amido- und imidoverbrückte Kupferkomplexe - Synthesen und Strukturen von [{Li(OEt2)}2][Cu(NPh2)3], [ClCuN(SnMe3)3], [{CuN(SnMe3)2}4],∞1[Cu16(NH2tBu)12Cl16], [{CuNHtBu}8], [Li(dme)3][Cu6(NHMes)3(NMes)2], [PPh3(C6H4)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}2] und [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8]

Reiß

Fenske

2000

Z. anorg. allg. Chem.

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Aus Reaktionen von stannylierten und lithiierten Aminen mit Salzen des ein‐ bzw. zweiwertigen Kupfers ließen sich amido‐ sowie imidoverbrückte Komplexe isolieren, die ein bis zwölf Kupferatome enthalten. Die einkernige Verbindung [{Li(OEt2)}2][Cu(NPh2)3] (1) entsteht durch Reaktion von CuCl mit LiNPh2 in Anwesenheit von Trimethylphosphan. Bei der Umsetzung von CuCl mit N(SnMe3)3 bildet sich der Donor‐Akzeptor‐Komplex [ClCuN(SnMe3)3] (2), welcher thermolytisch zu der tetrameren Verbindung [{CuN(SnMe3)2}4] (3) weiterreagiert. Alternativ kann 3 durch die Umsetzung von LiN(SnMe3)2 mit Cu(SCN)2 dargestellt werden. Der Amidoligand wirkt hier μ2‐verbrückend, während er in 1 terminal an das Kupferatom bindet. Der Einfluß der Abgangsgruppe am Alkylamid auf den Reaktionsverlauf zeigt sich beim Einsatz von Me3SnNHtBu bzw. LiNHtBu. Mit Me3SnNHtBu reagiert CuCl2 zu der polymeren Verbindung ∞1[Cu16(NH2tBu)12Cl16] (4). Das lithiierte Amin liefert dagegen sowohl mit CuCl als auch mit CuSCN den Komplex [{CuNHtBu}8] (5), welcher aus zwei zu 3 vergleichbaren, planaren Cu4N4‐Einheiten aufgebaut ist. Bei Einführung eines Mesitylrestes am Lithiumamid sind verschiedene Produkte zugänglich: Mit CuBr oder CuSCN erhält man den ionischen Komplex [Li(dme)3][Cu6(NHMes)3(NMes)2] (6), dessen Anion ein prismatisches Cu‐Gerüst mit μ2‐verbrückenden Amido‐ und μ3‐verbrückenden Imidoliganden besitzt. In Gegenwart von PPh4Cl führt die Umsetzung von Cu(SCN)2 mit LiNHMes über eine ortho‐Metallierung zur Bildung von [PPh3(C6H4)CuNHMes] (7). Aus der Dreikomponentenreaktion von CuSCN mit LiNHMes und LiNHPh können je nach den Reaktionsbedingungen der dimere Komplex [{[Li(dme)][Cu(NHMes)(NHPh)]}2] (8) oder der Cluster [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8] (9) isoliert werden. Das Anion in 9 besteht aus einem Cu‐Kuboktaeder mit μ3‐verbrückenden (NPh)2–‐Liganden. Die Verbindungen 1–9 wurden durch Einkristall‐Röntgenstrukturanalysen charakterisiert.

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“…[11] Similar Sn À N bond lengths are found in the ions [(Me 3 Sn) 2 NH 2 ] (av. 2.171(9) ) and [(Me 3 Sn) 3 NH] (2.168(3) ), [8] which clearly indicates that steric effects play only a subordinate role. This idea is supported by density functional calculations (DFT) on EL 3 and [EL 4 ] (E N, P; L silyl, stannyl) which show that in going from NL 3 to [NL 4 ] the MÀN bonds (M Si, Sn) become significantly longer than the corresponding MÀP bonds in the phosphorus analogues (Table 1).…”

Section: Matthias Driess* Christian Monse â Klaus Merz Und Christopmentioning

confidence: 87%

Perstannylated Ammonium and Phosphonium Ions: Organometallic Onium Ions That Are also Base-Stabilized Stannylium Ions

Drieß

Monsé

Merz

et al. 2000

Angew. Chem. Int. Ed.

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Weakly coordinating anions and nonpolar solvents facilitate the isolation of the first NH4+ and PH4+ derivatives completely substituted with main group organometallic units. The triflate and BPh4 salts of the [E(SnMe3)4]+ ions (E=N, P) undergo a rapid Me3Sn+ ion exchange in THF and thus represent base‐stabilized stannylium ions. The structure of the cation in [N(SnMe3)4]+[OSO2CF3]− is depicted.

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Elementorganisch substituierte Ammonium‐Salze. Die Kristallstrukturen von [HN(SnMe₃)₃]I, [H₂N(SnMe₃)₂][SnMe₃Cl₂] und [N(AsMe₃)₂]Br

Cited by 18 publications

References 18 publications

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Perstannylated Ammonium and Phosphonium Ions: Organometallic Onium Ions That Are also Base-Stabilized Stannylium Ions

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