A Comprehensive Investigation of a Zwitterionic Ge^I Dimer with a 1,2‐Dicationic Core

Abstract

The reductive dehalogenation of a zwitterionic GeII species to make a zwitterionic GeI dimer with a 1,2‐dicationic core is reported herein. To the root of the stability of this compound, the molecular and electronic structures were comprehensively characterized and investigated using crystallographic, spectroscopic, and computational methods. It was determined that the Ge centers are attracted because they are both electron‐rich and positively charged. A comparison to the electronic structure in triphosphenium cations revealed varying degrees of covalent bonding and that this difference can be distinguished spectroscopically.

Heavy Metals Make a Chain: A Catenated Bismuth Compound

“…If all of the crystallographic and computational resultsa re considered in total, it is possible to draw aL ewis type bonding modelf or compound 3 that agreesw ith most of the acquired information ( Figure 9). [31,32] The dative PÀBi bondss hown are consistentw ith the closed shell interactions found in the QTAIM calculations, while the BiÀCl bonds also likely have a charget ransfer component as suggested computationally.T he formal charges on the central Bi atoms (in conjunction with the lower overall coordination number of those atoms)a re in agreement with the shorter "inner" PÀBi distances and the longer central BiÀBi bond observed in the crystal structure. The formal oxidation state of the outer bismuth atoms is thus Bi II and that for the centralb ismuth atoms is Bi I ,w hich is consistent with the overall charge balance.…”

“…[12] The Bi-P phosphorus bonds in 3 fall into two distinct categories. The two inner bismuth centres (Bi2 and Bi3) form BiÀPb onds that are shorter (average 2.704(3) )t han those of the two terminal bismuth centres (Bi1 and Bi4) which average 2.739(3) .T he difference in the two bond lengths, 0.0345 ,i ss ignificant and suggestst hat the two types of BiÀPb onds in the structure could arise from different coordinationm odes.I na greement with this, the 31 Ps sNMR spectra reveal two distinct chemical environments with equal intensities and similar chemical shifts but very different line widths, likely relatedt os tructurald isorder and/or mobility.T he better resolved low fields ignal must arise from two similarb ut non-equivalent sites, while such a distinction is impossible for the high field signals.…”

“…Volatiles were removed under vacuum yielding small deep red plate crystals (40 mg, 5.4 %y ield);m .p. 191-193 (dec); 31…”

“…It seemed reasonable to assume that the BiCl 3 would first react with HN[P(iPr) 2 ] 2 to give HCl and BiCl 2 {N[P(iPr) 2 ] 2 }, the fragment seen in the final product. However,e vidence of this product was not observed spectroscopically.S omei nsightw as gained by studying the white slurry materialf ormed in the initial stage of the reactiona nd its 31 PNMR spectral data is includedi nt he SI. In those spectra the chemical shift of the white residue (39.9 ppm) is similar to that observedf or the PH atoms (39.3 ppm) of the cation in 2a.T he peak is split in the non-decoupled 31 Ps pectrum ( 1 J PH = 459 Hz versus 431 Hz in 2a)s uggesting the presence of PH groups in the white product as well.…”

Polymer networks functionalized with low‐valent phosphorus cations

“…previously reported data. [36] scanning calorimeter (DSC) was used to determine glass transition temperatures (T g ) with a ramp rate of 40 C per min. All T g values are reported using the onset temperature from the last heating cycle.…”