Cyclische Diazastannylene, XXIV. Zur Umsetzung von (tert‐Butylimino)stannylen mit Chlorwasserstoff

Abstract

(tert‐Butylimino)stannylen (1) reagiert mit Chlorwasserstoff zu [tBuN(H)–SnCl]2 (2a), tBuNH2 · SnCl2 (3) und tBuNH3⊕ SnCl3⊖ (4). Da die Trennung der kristallinen Produkte Schwierigkeiten macht, ist man auf Alternativsynthesen von 2a, 3 und 4 angewiesen. Me2Si[N(tBu)H][N(tBu)]SnX (6a: X = Cl, 6b: X = Br, 6c: X = I) stellt eine Ausgangsstufe dar, die mit tert‐Butylamin zu 2a (X = Cl) und 2b (X = Br) quantitativ umgesetzt werden kann. 3 und 4 entstehen aus 2a u.a. durch HCl‐Addition. 6a, b und c zeigen unterschiedliche 1H‐NMR‐Spektren in Abhängigkeit von der Temperatur, was auf eine intramolekulare Ligandenumordnung hinweist. Die Röntgenstrukturanalysen von 6a (orthorhombisch, Raumgruppe P112121), 3 (monoklin, P21/c, und triklin, P1) und 4 (triklin, P1) weisen 6a als Molekül mit einer intramolekularen Donor‐Akzeptor‐Bindung [Sn–N = 2.347(6) Å], 3 in beiden Modifikationen als Addukt von SnCl2 an tBuNH2 [Sn–N = 2.334(4) Å (monoklin) bzw. 2.338(4) Å (triklin)] und 4 als Ionenpaar tBuNH3⊕ SnCl3− mit H–Cl‐Brücken im Kristall aus [Sn–Cl = 2.542 (Mittelwert), C–N = 1.515(6) Å].

Three‐coordinate divalent Group 14 element derivatives and related compounds

“…Thus, the presence of ligands with donor side arms on the germanium or the tin element can (by transfer of electron density) reduce the deficit on 37 is, to our knowledge, the first example of an intramolecular base stabilized homoleptic dialkylgermylene. Various amino-, phosphino-, thioalkoxy-, alkoxy-and aryloxy-divalent species have also been isolated in monomeric form owing to this method of stabilization; one should mention in particular the studies of Jutzi and co-workers, 28,32,54,71 Veith and coworkers, 15,18,40,66 Parkin and co-workers, 67 Jurkschat and co-workers, 77,78 Dias and co-workers 31,35,42,69,80,81 and Roesky and co-workers. …”

N → Sn coordination in the complexes of tin halides with pyridine: A comparison between Sn(II) and Sn(IV)

“…Figure presents examples of crystal structures in which SnCl n is coordinated by N‐donor ligand(s), other than pyridine. These examples illustrate tri‐ and tetra‐coordinated Sn(II) centers (refcodes: GEHTOC and FEDYES), and penta‐ and hexa‐coordinated Sn(IV) centers (refcodes: IZETEM and IZETAI).…”

New stable germylenes, stannylenes, and related compounds. 8. Amidogermanium(II) and ‐tin(II) chlorides R2N‐E14‐Cl (E14 = Ge, R = Et; E14 = Sn, R = Me) revealing new structural motifs

“…The planes formed by two carbon and nitrogen atoms of the bridging amido groups are at the angles of 81.0(1) and 82.1 (2) • , respectively, with respect to the E Although the structures of 1 and 2 are very similar, there are two striking distinctions between them. First, the conformations of the E 14 2 N 2 four-membered rings are obviously different.…”

“…This might indicate additional stabilization of compound 2 by the formation of the Sn· · ·Cl intramolecular coordination, as it was found for compound 9. 2 However, unlike 9, no such an inward shift is observed in the crystal of 2 due to the absence of steric hindrances at the metal atom, which favors the formation of intermolecular interactions between the chloride atom and the metal atom of a neighboring molecule.…”

“…8 Moreover, the use of 8 as a precursor for the reductive elimination yielded the first body-centered 15-membered Group 14 metal cluster-bearing amido ligands, whereas the analogous reactions of 6 and 7 gave rise to elemental tin and a tar of unidentified content, respectively. 5 The present paper is a contribution to the chemistry of thermally stable amidogermanium(II) and -tin(II) chlorides Et 2 N-Ge-Cl (1) and Me 2 N-Sn-Cl (2), in which the E 14 (E 14 = Group 14 element) centers bear small diethylamino or dimethylamino ligands. No X-ray crystal structures of divalent Group 14 chlorides with smaller alkylamino substituents have been published so far.…”