Insertion of Cp*GeCl into a Tungsten−Chlorine Bond and Crystal Structures of the Germylenes Cp*GeCl, [Cp*GeBr]₂, and [Cp*Ge][BF₄] (Cp* = Pentamethylcyclopentadienyl)

Abstract

Insertion of the chlorogermylene Cp*GeCl (2) (Cp* = pentamethylcyclopentadienyl) into the W−Cl bond of CpW(CO)3Cl (1) (Cp = cyclopentadienyl) affords the germyl complex CpW(CO)3GeCl2Cp* (3). Treatment of GeCp*2 with 1 equiv of HBr gives the bromogermylene [Cp*GeBr]2 (5). The crystal structures of the halogermylenes 2 and 5 are described. 2 is monomeric in the solid-state, whereas 5 has a dimeric structure, which is characterized by two germylene units associated through asymmetric bromo bridges. In both compounds the pentamethylcyclopentadienyl group is bonded to the germanium atom in an asymmetric η2 fashion. In comparison, the crystal structure of [Cp*Ge][BF4] (6) reveals the presence of BF4 anions and Cp*Ge cations, in which the Cp* ligand is η5 bonded to the germanium atom.

Reactive p-block cations stabilized by weakly coordinating anions

“…In 2005, the structure of the [(C 5 Me 5 )Sn][B(C 6 F 5 ) 4 ] was determined in which these interactions are a lot weaker 375 and with the same anion, [(C 5 Me 5 )Pb] + was synthesized and structurally characterized. 375 The sole exception is germanium, whose [(C 5 Me 5 )Ge] + was only characterized by XRD with [BF 4 ] – 376 and [SnCl 3 ] – 377 as its counterion and not with any larger WCA. In addition, interesting triple-decker cations are known for tin and lead: [({Me 5 C 5 }Sn) 2 (μ-Me 5 C 5 )] + was first synthesized and structurally characterized with the [Ga(C 6 F 5 ) 4 ] – anion, 378 its structure was subsequently published with [B(C 6 F 5 ) 4 ] – together with the analogous lead compound ( Fig.…”

Synthesis and characterization of β-diketiminate germanium(II) and tin(II) bromides

“…Cp*GeCl was the first example of a monohalide with the general composition RMX (M = Ge, Sn; R = organic group; X = halide) prepared in 1987 [2], followed by the tin analogue RSnCl (R = C(SiMe 3 ) 2 C 5 H 4 N-2) in 1988 [3]. After 10 years Filippou et al were successful in preparing a germanium bromide dimer, [Cp*GeBr] 2 [4]. In 2006 our group reported the synthesis and structure of the first monomeric chloro silylene [{PhC(NtBu) 2 }SiCl] [5].…”

“…Anisotropic displacement parameters are depicted at the 50% probability level and all hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (°): Ge1-Br1 2.5064(3), Ge1-N1 1.9934(14), N1-C25 1.326(2); N1-Ge1-N2 90.80(6), N1-Ge1-Br1 92.58(4), and Ge1-N1-C25 124.91(11).…”

Germanium Organometallic Compounds: Classification and Analysis of Crystallographic and Structural Data

“…The data for fifty organogermaiium compounds with cboidination number five are givai in Table The crystal lattice of a pale yellow derivative [20] is characterised by a pentagonal bipyramidal cations [Ge(r| -C 5 Me 5 )] and BF 4 anions TheC 5 Me 5 group is pentahapto-coordinated to the Ge atom with mean Ge-C distance Clive Ε. Η oll cm ay and Milan Melnik Germanium Organometallic Compounds: Classification And Analysis of Crystallographic and Structural Data of 225.5(3) pm (range (224.6(2) -226.1(2) pm). The Ge-C(caitroid) distance is 189.7 pm.…”

“…The data in Table 4 shows that Ge(II) occurs with pentahapto C-donor ligaids (hemi-sandwiched) in a pentagonal geometry [20,179] There are three examples [204,205,211] whidi contain two ciystallogiaphically independent molecules in one crystal. These differ mostly by degree of distortion and represent distortion isomerism [11}…”