A Digermanium(III) 1,2-Dication Stabilized by Amidinate and cAAC-Phosphinidenide Ligands.

A digermanium(III) 1,2-dication comprises two cationic centers located at two interconnected Ge atoms. The strong Coulombic repulsion between two positively charged germanium cations hinders their bond formation. Balancing these two oppositions was achieved by using amidinate and cyclic (alkyl)amino carbene (cAAC)-phosphinidenide ligands, where an amidinato cAAC-phosphinidenidogermylene complex, [LGeP(cAAC)] (, where L = PhC(NBu), cAAC = :C{C(Me)CHC(Me)NAr}, and Ar = 2,6-PrCH), underwent one-electron oxidation with a bis(phosphinidene) radical cation, [(cAAC)P], to form a digermanium(III) 1,2-dication, [LGeP(cAAC)], in compound .

Stannylene cyanide and its use as a cyanosilylation catalyst.

Two routes can offer the first stannylene cyanide [(L)SnCN] (5); the substitution reaction of either stannylene amide [(-Bu)ATISnN(SiMe)] (3) or stannylene pyrrolide [(-Bu)ATISn(NCH)] (4) using an excess of trimethylsilyl cyanide (L = aminotroponiminate (ATI)). Using 0.1-2.

Ge(ii) cation catalyzed hydroboration of aldehydes and ketones.

Well-defined germylene cations [(i-Bu)2ATI]GeOTf (4) and [(i-Bu)2ATIGe][GaCl4] (5) are isolated, and the catalytic utility of compound 4 for the hydroboration of a variety of aldehydes and ketones is reported (ATI = aminotroponiminate).

Diverse Bonding Activations in the Reactivity of a Pentaphenylborole toward Sodium Phosphaethynolate: Heterocycle Synthesis and Mechanistic Studies.

The reaction of the pentaphenylborole [(PhC)BPh] (1) with sodium phosphaethynolate·1,4-dioxane (NaOCP(1,4-dioxane)) afforded the novel sodium salt of phosphaboraheterocycle 2. It comprises anionic fused tetracyclic P/B-heterocycles that arise from multiple bond activation between the borole backbone and [OCP]anion. Density functional theory calculations indicate that the [OCP] anion prefers the form of phosphaethynolate O-C≡P over phosphaketenide O═C═P to interact with two molecules of 1, along with various B-C, C-P, and C-C bond activations to form 2.

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.

Use of thio and seleno germanones as ligands: silver(I) halide complexes with Ge═E→Ag-I (E = S, Se) moieties and chalcogen-dependent argentophilic interaction.

The potential of thio and seleno germanones [LPhGe═E] (L = aminotroponiminate (ATI) ligand, E = S 3, Se 4) to function as ligands has been demonstrated through the isolation of their silver(I) iodide complexes [{(t-Bu)2ATIGe(E)Ph}2(Ag2I2)] (E = S 5, Se 6) with a planar and discrete Ag2I2 core. Compounds 5 and 6 possess the hitherto unknown Ge═E→Ag-I moieties and the crystallographic data reveals the presence of a strong argentophilic interaction (2.950(1) Å) in complex 6, but is inconclusive in complex 5 (3.

Germylene cyanide complex: a reagent for the activation of aldehydes with catalytic significance.

The first example of a germanium(II) cyanide complex [GeCN(L)] (2) (L=aminotroponiminate (ATI)) has been synthesized through a novel and relatively benign route that involves the reaction of a digermylene oxide [(L)Ge-O-Ge(L)] (1) with trimethylsilylcyanide (TMSCN). Interestingly, compound 2 activates several aldehydes (RCHO) at room temperature and results in the corresponding cyanogermylated products [RC{OGe(L)}(CN)H] (R=H 3, iPr 4, tBu 5, CH(Ph)Me 6). Reaction of one of the cyanogermylated products (4) with TMSCN affords the cyanosilylated product [(iPr)C(OSiMe3 )(CN)H] (7) along with [GeCN(L)] quantitatively, and insinuates the possible utility of [GeCN(L)] as a catalyst for the cyanosilylation reactions of aldehydes with TMSCN.

Are ligand-stabilized carboxylic acid derivatives with Ge═Te bonds isolable?

The stability of ligand-stabilized carboxylic acid derivatives (such as esters, amides, anhydrides, and acid halides) with terminal Ge═Te bonds is highly questionable as there is no report on such compounds. Nevertheless, we are able to isolate germatelluroester [LGe(Te)Ot-Bu] (4), germatelluroamide [LGe(Te)N(SiMe3)2] (5), and germatelluroacid anhydride [LGe(Te)OGe(Te)L] (6) complexes (L = aminotroponiminate (ATI)) as stable species. Consequently, the synthetic details, structural characterization, and UV-vis spectroscopic and theoretical studies on them are reported for the first time.

Aminotroponiminato(chloro)germylene stabilized copper(I) iodide complexes: synthesis and structure.

Reaction of an aminotroponiminato(chloro)germylene [(i-Bu)2ATIGeCl] (1) (ATI = aminotroponiminate) with CuI in acetonitrile afforded an aminotroponiminato(chloro)germylene stabilized copper(I) iodide complex [{(i-Bu)2ATIGeCl}2(Cu4I4)(CH3CN)2] (2) with a tetrameric distorted cubane type Cu4I4 core. The reaction of compound 1 in dichloromethane with CuI in the presence of 2 equiv of pyridine resulted in the first germylene stabilized copper(I) iodide complex [{(i-Bu)2ATIGeCl}(CuI)(C5H5N)2] (3) with a monomeric CuI core. A reaction of compound 1 with equimolar amounts of CuI and pyridine in dichloromethane resulted in a copper(I) iodide complex [{(i-Bu)2ATIGeCl}2(Cu2I2)(C5H5N)2] (4) with a dimeric Cu2I2 core.

Digermylene oxide complexes: facile synthesis and reactivity.

A simple heating of aminotroponiminate (ATI) ligand stabilized germylene monochlorides [(R)2ATIGeCl] (R = t-Bu 1, i-Bu 2) with an excess of potassium hydroxide in toluene resulted in the first ATI ligand stabilized digermylene oxides [{(R)2ATIGe}2O] (R = t-Bu 3, i-Bu 4), respectively. Reaction of compound 3 with elemental sulfur and selenium gave the first germaacid anhydride complexes [{(t-Bu)2ATIGe(E)}2O] (E = S 5, Se 6) with (S)Ge-O-Ge(S) and (Se)Ge-O-Ge(Se) moieties, respectively. The digermylene oxide complexes 3 and 4 and germaacid anhydride complexes 5 and 6 were characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffraction analysis.

Aminotroponiminatogermaacid halides with a Ge(E)X moiety (E = S, Se; X = F, Cl).

Fluorination of aminotroponiminate (ATI) ligand-stabilized germylene monochloride [(t-Bu)(2)ATI]GeCl (1) with CsF gave the aminotroponiminatogermylene monofluoride [(t-Bu)(2)ATI]GeF (2). Oxidative addition reaction of compound 2 with elemental sulfur and selenium led to isolation of the corresponding germathioacid fluoride [(t-Bu)(2)ATI]Ge(S)F (3) and germaselenoacid fluoride [(t-Bu)(2)ATI]Ge(Se)F (4), respectively. Similarly, reaction of aminotroponiminatogermylene monochloride [(i-Bu)(2)ATI]GeCl (9) with elemental sulfur and selenium gave the aminotroponiminatogermathioacid chloride [(i-Bu)(2)ATI]Ge(S)Cl (11) and aminotroponiminatogermaselenoacid chloride [(i-Bu)(2)ATI]Ge(Se)Cl (12), respectively.