Aminotroponiminatogermaacid Halides with a Ge(E)X Moiety (E = S, Se; X = F, Cl)
DSpace at IIT Bombay
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Title |
Aminotroponiminatogermaacid Halides with a Ge(E)X Moiety (E = S, Se; X = F, Cl)
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Creator |
SINHABABU, S
SIWATCH, RK MUKHERJEE, G RAJARAMAN, G NAGENDRAN, S |
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Subject |
N-HETEROCYCLIC GERMYLENES
MOLECULAR CALCULATIONS STABILIZED GERMYLENE ORBITAL METHODS TIN-COMPOUNDS COMPLEXES GERMANIUM DERIVATIVES ELEMENTS CHEMISTRY |
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Description |
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 aminotroponiminatogermaselenoacicl chloride [(i-Bu)(2)ATI]Ge(Se)Cl (12), respectively. Compound 9 has been prepared through a multistep synthetic route starting from 2-(tosyloxy)tropone S. All compounds (2-4 and 6-12) were characterized through the multinuclear NMR spectroscopy, and single-crystal X-ray diffraction studies were performed on compounds 2, 4, and 8-12. The germaselenoacid halide complexes 4 and 12 showed doublet (-142.37 ppm) and singlet (-213.13 ppm) resonances in their Se-77 NMR spectra, respectively. Germylene monohalide complexes 2 and 9 have a germanium center in distorted trigonal pyramidal geometry, whereas a distorted tetrahedral geometry is seen around the germanium center in germaacid halide complexes 4, 11, and 12. The length of the Ge=E bond in germathioacid chloride (11) and germaselenoacid halide (4 and 12) complexes is 2.065(1) and 2.194(av) angstrom, respectively. Theoretical studies (based on the DFT methods) on complexes 4, 11, and 12 reveal the nature of the Ge=E multiple bond in these germaacid halide complexes with computed Wiberg bond indices (WBI) being 1.480, 1.508, and 1.541, respectively.
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Publisher |
AMER CHEMICAL SOC
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Date |
2014-10-14T17:44:41Z
2014-10-14T17:44:41Z 2012 |
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Type |
Article
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Identifier |
INORGANIC CHEMISTRY, 51(17)9240-9248
http://dx.doi.org/10.1021/ic300715y http://dspace.library.iitb.ac.in/jspui/handle/100/14600 |
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Language |
en
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