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Digermylene Oxide Complexes: Facile Synthesis and Reactivity

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Title Digermylene Oxide Complexes: Facile Synthesis and Reactivity
 
Creator SIWATCH, RK
YADAV, D
MUKHERJEE, G
RAJARAMAN, G
NAGENDRAN, S
 
Subject GE SINGLE BOND
STABILIZED GERMYLENE
MOIETY E
GERMANIUM
DERIVATIVES
CHEMISTRY
ALKYNE
GROUP-14
ELEMENTS
ANALOGS
 
Description A simple heating of aminotroponiminate (ATI) ligand stabilized germylene monochlorides [(R)(2)ATIGeCl] (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)(2)ATIGe}(2)O] (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)(2)ATIGe(E)}(2)O] (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. In its Se-77 NMR spectrum, compound 6 showed a resonance at -78.9 ppm. The Ge-O-Ge bond angles in compounds 5 and 6 are 178.66(2)degrees and 179.81(2)degrees, respectively. To understand further the bonding features, DFT calculations followed by MO, AIM, and NBO analysis were carried out on compounds 3, 5, and 6. The computed Wiberg bond indices of Ge-O bonds are slightly less than 0.5 in all the aforementioned compounds, and the same for the Ge=E bonds in compounds 5 and 6 are close to 1.4.
 
Publisher AMER CHEMICAL SOC
 
Date 2014-10-14T17:42:39Z
2014-10-14T17:42:39Z
2013
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 52(23)13384-13391
0020-1669
1520-510X
http://dx.doi.org/10.1021/ic401720e
http://dspace.library.iitb.ac.in/jspui/handle/100/14596
 
Language en