Synthesis of tricyclic 1,4-dihydro-1,4-phosphagermines - trying to establish molecular fencing of reactive centers.

Novel tricyclic 1,4-dihydro-1,4-phosphagermines (3a and 4a) were synthesised from Ge(NR2)2-bridged 1,3-imidazole-2-thione derivative 2a; all structures were crystallographically confirmed. In going from rather small alkyl substituents (Me, nBu) at the nitrogen centers of the 1,3-imidazole-2-thione units to sterically more demanding R = Mes and changing the employed Ge reagent from (R2N)2GeCl2 to R2NGeCl3 we achieved access to mixed functional bis(1,3-imidazole-2-thione)-substituted germanium derivative 2c. The latter was treated with MeLi and, subsequently, with PCl3 to yield a pentacyclic P,Ge-heterocycle (5); its formation was rationalized using DFT theoretical calculations.

(NHC)Si═C═N-R: A Two-Coordinated Si0-Isocyanide Compound as Si(NHC) Transfer Reagent.

Experimental and theoretical studies are reported of the first two-coordinated Si0-isocyanide compound (SIDipp)Si═C═N-ArMes (1: SIDipp (NHC) = C[N(Dipp)CH2]2, ArMes = 2,6-dimesitylphenyl), supported by an N-heterocyclic carbene (NHC). A Si atom economic two-step synthesis of 1 involves a 2e reduction of the isocyanide-stabilized silyliumylidene salt [SiBr(CNArMes)(SIDipp)][B(ArF)4] (2[B(ArF)4], ArF = B(C6H3-3,5-(CF3)2)4) with KC8. 2[B(ArF)4] was obtained from SiBr2(SIDipp) after bromide abstraction with an equimolar mixture of Na[B(ArF)4] and ArMesNC. Exact adherence to the stoichiometry is crucial in the latter reaction, since 2[B(ArF)4] reacts with SiBr2(SIDipp) via isocyanide exchange to afford the disilicon(II) salt [Si2Br3(SIDipp)2)][B(ArF)4] (3[B(ArF)4]), the reaction leading to an equilibrium that favors 3[B(ArF)4] (Keq(298 K) = 10.6, ΔH° = -10.6 kJ mol-1; ΔS° = -16.0 J mol-1 K-1). 3[B(ArF)4] was obtained selectively from the 2:1 reaction of SiBr2(SIDipp) with Na[B(ArF)4] and fully characterized. Detailed studies of 1 reveal an intriguing structure featuring a planar CNHC-Si-C-N skeleton with a V-shaped geometry at the dicoordinated Si0 center, a slightly bent Si═C═N core, a CNHC-Si-CCNR 3c-2e out of plane π-bond (HOMO), and an anticlinal conformation of the SIDipp and ArMes substituents leading to axial chirality and the presence of two enantiomers, (Ra)-1 and (Sa)-1. Compound 1 displays structural dynamics in solution, rapidly interconverting the enantiomers. The silacumulene 1 is a potent Si(SIDipp) transfer agent as demonstrated by the synthesis and full characterization of the NHC-supported germasilyne (Z)-(SIDipp)(Cl)Si═GeArMes (4) from 1 and Ge(ArMes)Cl.

The Preparation of Complexes of Germanone from a Germanium µ-Oxo Dimer.

Complexes of germanone containing formal Ge=O→M bonds (M=Zn, B, Ge, Sn) were isolated and characterized. The compounds were prepared through a novel synthetic route using a germanium µ-oxo dimer 3 as the starting material. This method circumvents the need to employ germanones to prepare complexes of germanones.

O,S-Heterocyclic stannylenes: synthesis and reactivity.

Commercially available N-oxide (2-mercaptopyridine-N-oxide) is used as a ligand instead of an oxidizing agent to stabilize the compounds of main group elements in low-valent states. The isolated compounds [(C5H4NOS)2Sn (), (C5H4NOS)SnCl () and (C5H4NOS)GeCl ()] are the first structurally characterized examples of O,S-heterocyclic stannylenes and germylenes with interesting bonding features. Further, the reaction of compound with SbCl3 afforded the rare dichlorodiantimony oxide [{(C5H4NOS)SbCl}2O] () unprecedentedly.

Digermylene Oxide Stabilized Group 11 Metal Iodide Complexes.

Use of a substituted digermylene oxide as a ligand has been demonstrated through the isolation of a series of group 11 metal(I) iodide complexes. Accordingly, the reactions of digermylene oxide [{(i-Bu)2ATIGe}2O] (ATI = aminotroponiminate) (1) with CuI under different conditions afforded [({(i-Bu)2ATIGe}2O)2(Cu4I4)] (2) with a Cu4I4 octahedral core, [({(i-Bu)2ATIGe}2O)2(Cu3I3)] (3) with a Cu3I3 core, and [{(i-Bu)2ATIGe}2O(Cu2I2)(C5H5N)2] (4) with a butterfly-type Cu2I2 core. The reactions of compound 1 with AgI and AuI produced [({(i-Bu)2ATIGe}2O)2(Ag4I4)] (5) with a Ag4I4 octahedral core and [{(i-Bu)2ATIGe}2O(Au2I2)] (6) with a Au2I2 core, respectively. The presence of metallophilic interactions in these compounds is shown through the single-crystal X-ray diffraction and atom-in-molecule (AIM) studies. Preliminary photophysical studies on compound 6 are also carried out.

Single-step conversion of silathiogermylene to germaacid anhydrides: unusual reactivity.

A novel silathiogermylene [Bu(I)2(ATI)GeSSiMe3] (2) containing a reactive Ge(II)-SSiMe3 moiety showed an unusual reaction when treated with elemental selenium and sulfur to afford the germaacid anhydrides [{Bu(I)2(ATI)Ge(Se)}2Se] (3) and [{Bu(I)2(ATI)Ge(S)}2S] (4) in excellent yields, respectively. This single-step conversion of compound 2 to compounds 3 and 4 involves condensation along with insertion and oxidative addition reactions and such reactivity of a germylene with elemental chalcogens is observed for the first time.

Can low-valent germanium chemistry be practiced under ambient conditions? A tale of a water-stable yet reactive germylene monochloride complex.

A germylene monochloride complex ((DPM)GeCl, 1) that is water stable was isolated for the first time. Interestingly, it reacts with cesium fluoride under ambient conditions (non-inert atmosphere and water-containing solvent) to afford water stable germylene monofluoride complex ((DPM)GeF, 2). Due to the usage of DPM (dipyrrinate) ligand, germylene monohalides 1 and 2 show fluorescence in the visible region at 555 and 538 nm, respectively. Compounds 1 and 2 are the first fluorescent germylene complexes and were characterized by multinuclear NMR spectroscopy. The structure of compound 1 was also proved by single crystal X-ray diffraction studies.