A Silylene‐Stabilized Germanium Analogue of Alkynylaluminum

Abstract

In contrast to the well-developed metal acetylides, the heavier analogues of the type REEM (E = Si, Ge, Sn, Pb; M = metals) have not been reported to date. Herein, we describe the synthesis of a silylenestabilized germanium analogue of alkynylaluminum ( 4) by the reaction of a silylene-stabilized digermavinylidene (3) with 0.25 equiv of (AlCp*) 4 in THF at 80 °C. The structure of 4 has been unambiguously characterized by spectroscopic analysis, X-ray diffraction analyses and DFT calculations, and features a linear AlGeGe skeleton with a Ge=Ge double bond and a polarized GeÀ Al bond. Complex 4 shows excellent reactivity towards small molecules such as H 2 , CS 2 and TolNCO, and this allows for the construction of the structurally intriguing germylenyl aluminum complex (5) and the germacycles (6, 7).

Double 1,2‐Carbon Migration at Mixed Heavier Sn=Ge Vinylidenes

“…In comparison with the homonuclear dimetallynes, [24] the synthesis of heteronuclear heavier alkynes is a challenging task [25] . The facile 1,2‐carbon migration in 3 might make it a suitable precursor for the synthesis of aluminyl stannagermyne by the insertion of an Al(I) species into the Ge−C bond, which is similar to the method employed to synthesize an aluminyl digermyne [7a] . Treatment of 3 with 0.25 equiv.…”

An Isolable Bis(Germylene)‐Stabilized Plumbylone

“…have been shown to possess unusual coordination modes and reactivity as a result of their ambiphilic character [16] . Utilizing a terphenyl‐germylene–silylene ligand, we recently isolated the first germanium analogue of alkynylaluminum [17] . Herein, we describe use of a bidentate terphenylgermylene ligand to support the target plumbylone.…”

“…[16] Utilizing a terphenylgermylene-silylene ligand, we recently isolated the first germanium analogue of alkynylaluminum. [17] Herein, we describe use of a bidentate terphenylgermylene ligand to support the target plumbylone. The reaction of dilithio-ocarborane with 2 equiv of chlorogermylene (C 6 H 3 -2,6-Trip 2 )GeCl (Trip = 2,4,6-triisopropylphenyl) [18] afforded a cyclic digermene (1) in 72 % yield as purple crystals.…”

Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

“…In this regard, the metal complexes that are equipped with polydentate ATs have been generally prepared from metal-free ATs (generically E(R 1 NC(R 2 )NR 1 )X; E = heavier tetrel atom, X = anionic group; see Figure ) functionalized with at least one additional donor group (D). Figure shows the currently known types of metal-free potentially polydentate ATs, − which formally result from (a) attaching a donor fragment to the E atom (X position; type I ), − (b) connecting with a linker, which can also have additional donor or prone to undergo metalation groups, two ATs through their E atoms (X position; type II ), − through the amidinate central C atoms (R 2 position; type III ) − or through one of the two amidinate N atoms (R 1 position; type IV ), and (c) attaching a donor fragment to one of the N atoms (R 1 position; type V ). , By far, types I and II , whose syntheses normally imply an easy Cl replacement with an appropriate lithiated group on well-known chlorido-ATs, are the most explored donor-functionalized ATs, having led to a great variety of metal complexes fitted with κ 2 E , D -, − κ 2 E , E -, , κ 3 E , D , E -, κ 3 E , C , E - ligands, many of them with catalytic applications . On the other hand, the functionalization pathways that lead to types III , IV , and V , which imply modifications on the amidinate skeleton befor...…”