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

Aminostannanes and aminostannylenes containing a C,N-chelated ligand

“…These compounds are chloro aminogermylene and aminostannylene of formulae R 2 NeE 14 eCl (E 14 ¼ Ge or Sn) which form dimers through the singly of doubly bridging amino ligands, with terminal chloro ligands in mutual trans configuration. When compared to 6, the tin compound of Khrustalev [24], (Me 2 NeSneCl) 2 , has an almost planar Sn 2 N 2 ring and a trans configuration of the SneCl bonds. The same orientation of SneCl bonds in 5 could be explained by the discrepancy in steric bulk of the nitrogen substituents.…”

Oxidative Addition of Alkyl Iodides to [Sn(NMe2)2]2: In Situ Generation of RSn(NMe2)3 Compounds

“…[ISn­(NMe 2 )] 2 ( 2 ) is independently synthesized by combining equimolar amounts of SnI 2 and 1 in THF, similar to the procedure to make the analogous [ClSn­(NMe 2 )] 2 . The stannous amide/iodide is sparingly soluble in nonpolar solvents, e.g., benzene and hexanes; however, it dissolves readily in THF.…”

Linking Low-Coordinate Ge(II) Centers via Bridging Anionic N-Heterocyclic Olefin Ligands

“…Computational studies also explain our inability to access an inorganic alkyne RGeGeR upon reduction of the Ge­(II) chloride precursor [( Me IPrCH)­GeCl] 2 ; this observation can be linked to the high propensity of the reported anionic NHO ligand to form bridging isomers leading to the eventual extrusion of Ge via the isomer R 2 GeGe . While the bridging of two Ge­(II) centers via anionic heteroatom-based ligands to yield dimeric [(μ-R′)­GeCl] 2 species (e.g., R′ = - NR 2 , -PR 2 , -OR, or -SR) is known, herein we show that added interactions between the linked Ge­(II) centers in the form of bridging Ge–Cl–Ge and Ge–H–Ge interactions are possible, opening the door for possible cooperative activation of substrates in catalysis.…”