Open‐Shell Complexes Containing Metal–Germanium Triple Bonds

Synthesis and Structural Characterization of Metallogermylenes, Cp-Substituted Germylene, and a Germanium(II)-Borane Adduct from Pyridyl-1-azaallyl Germanium(II) Chloride

“…By addition of AlH 3 ·NMe 3 or [K{B(Bu i ) 3 }H] to a β-diketiminato germanium(II) chloride, a stable monomeric terminal germanium(II) monohydride was synthesized by Roesky, and the germanium(II) hydride has played an important role in synthetic chemistry and the activation of small molecules . In addition, the versatile chlorogermylenes were also employed in the formation of unusual hetero-bimetallic metal–metal bonded systems, which provide valuable structural information on the metal complexes supported by monodentate or bidentate ligands . The aforementioned reports are only some highlights of the importance of heteroleptic germanium(II) chlorides in low-valent germanium chemistry, and it is not surprising that there is still intensive research activity focused on developing new ligands for stabilization of the low-valent germnaium(II) center in RGeCl or the continuation of the reactivity study of chlorogermylenes …”

Carbon, silicon, germanium, tin and lead

“…The paper also reports EPR data showing a really quite anistropic environment. 100 The potential for silicon(II) to act as a ligand has been explored in two papers that have appeared this year. In both cases, the lithium salt of a dianion reacts with the well-known PhC(NBu t ) 2 M(14)Cl to give either 1,1 0 -{PhC(NBu t ) 2 M(14)} 2 -ferrocene (M(14) = Si, Ge) 101 or 1,3-{PhC(NBu t ) 2 SiO} 2 -4,6-Bu t 2 -resorcinol.…”

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

“…reported a variety of compounds exhibiting a triple bond between a transition metal (M=Nb, Cr, Mo, W, Mn, Re, Fe, Ni, Pt) and a heavy element of the Group 14 (E=Si, Ge, Sn, Pb) [3] . Three synthetic strategies for the synthesis of these carbyne homologues were reported: nucleophilic substitution at organotetrel halides by nucleophilic transition metal complexes; [1, 2, 3c,i] elimination of N 2 /PMe 3 ligands and oxidative addition of organotetrel halides at transition metal complexes [3f,g,k–q] and formation of haloylidene complexes followed by halide abstraction [3d,e] . Hashimoto, Tobita and co‐workers have synthesized tungsten germylyne and tungsten silylyne complexes by dehydrogenation using mesityl isocyanate, nitriles or stepwise proton and hydride abstraction with the hydrido hydrogermylene and hydrido hydrosilylene as starting materials [4] .…”