Products of the Reactions of 2-Diazomalonate and of 2-Diazoindanedione with Germylenes and Stannylenes

Abstract

Products obtained in the reaction between germylenes or stannylenes with dimethyl 2-diazomalonate and 2-diazo-1,3-indanedione have been isolated and characterized. Compounds thus prepared are the 2H-1,3,4,2-oxadiazagermanine-5-carboxylates 1 and 2, the indeno[2,1-e]-1,3,4,2-oxadiazametallanin-5(2H)-ones 7 and 8, the 6-oxa-3,4-diaza-2,7digermabicyclo[3.2.0]hept-3-ene-carboxylate 3, resulting from the thermal treatment of 2, and the unsymmetrical dimer of 7, (7) 2 . Furthermore the reaction products of 2 with t-BuNCO, 4, with PhCHO, 5, and with H 2 CdCHCHO, 6, and compound 9 obtained by partial hydrolysis of 7 and (7) 2 were isolated. The compounds were characterized by NMR spectroscopy ( 1 H, 13 C, and 29 Si and in part 15 N and 119 Sn), MS (EI or FI), and elemental analyses. X-ray crystal structure determinations are presented for 1, 2, 3, 4, and (7) 2 .

The First Zwitterionic Dinuclear Germanium(IV) Complex with Pentacoordinate Germanium Atoms: Synthesis and Crystal Structure Analysis

“…After the solvent and excess triethylamine were removed under reduced pressure, n-pentane (300 mL) was added and the mixture was kept at room temperature for 2 h. The precipitate was filtered off, the filtrate was concentrated under reduced pressure, and the oily residue was distilled in vacuo (Kugelrohr distillation; oven temperature 250°C, 0.01 Torr) to give 7 in 60% yield as a colorless liquid (9.89 g, 22.3 mmol). 1 6.82;N,6.32. Found: C,32.4;H,7.0;N,6.2. Crystal Structure Analysis of 5a‚8H2O.…”

“…1 6.82;N,6.32. Found: C,32.4;H,7.0;N,6.2. Crystal Structure Analysis of 5a‚8H2O. A suitable single crystal of 5a‚8H2O was obtained by crystallization of 5a from water at room temperature (slow evaporation of the solvent).…”

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

“…The solid-state structure of 12 showed a tetrahedral germanium center bearing a κ 2 -N,O-oxazacyclobutane ligand (Figure 6). Although this general class of ligand has only been reported once with germanium, 62 and formed in an entirely different pathway, similar chemistry is observed upon treatment of titaniumimido or nickelimido complexes with benzaldehyde. 63,64 Interestingly, treatment of [(BDI)Al] (BDI = {N(Dipp 3 )C(Me)} 2 CH) with benzophenone followed by addition of trimethylsilyl azide also gives the κ 2 -N,Ooxazagcyclobutane ligand.…”

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

“…Eighteen examples of trigonal bipvramidal geometry are seen in Table 4 and all but one of these exhibit a high degree of distortion due to the incorporation of bidentate groups [68,69], bi-and tridentate groups [71,72], tridentate groups [60,70,82] and tetradentate groups [73][74][75][76]80,81] which span the equatorial and axial positions. The remaining example [79] has five unidentate ligands and consequently the lowest degree of distortion in this series.…”

“…[7,126,127] in which a pair of bidentate ligands. Finally, in yellow derivative [60] the μ-η -iodam serves as a bridge between two equivalent {(Me2Si)2N}2Ge moieties. Finally, in yellow derivative [60] the μ-η -iodam serves as a bridge between two equivalent {(Me2Si)2N}2Ge moieties.…”