N-heterocyclic germylene-metal adducts

The N-heterocyclic chlorogermylene and chlorostannylene of composition [L"E" ̈Cl] (E = Ge, Sn; L = PhC(NtBu)2) is a Lewis bases due to the stabilization of the metal centres’ empty orbitals being stabilized by the lone pair electrons on the nitrogen atom of the ligand. Further stabilizati...

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Main Author: Leong, Bi Xiang
Other Authors: So Cheuk Wai
Format: Thesis
Language:English
Published: 2016
Subjects:
Online Access:http://hdl.handle.net/10356/68970
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author Leong, Bi Xiang
author2 So Cheuk Wai
author_facet So Cheuk Wai
Leong, Bi Xiang
author_sort Leong, Bi Xiang
collection NTU
description The N-heterocyclic chlorogermylene and chlorostannylene of composition [L"E" ̈Cl] (E = Ge, Sn; L = PhC(NtBu)2) is a Lewis bases due to the stabilization of the metal centres’ empty orbitals being stabilized by the lone pair electrons on the nitrogen atom of the ligand. Further stabilization was reinforced by replacing the Cl atom by the bulky and electron-donating bis(trimethylsily)amide substituent to form [L"E" ̈N(SiMe3)2] (E = Ge, Sn). In order to demonstrate the Lewis basicity of these compounds, [LGeN(SiMe3)2] was reacted with Lewis acidic borane to afford the N-heterocyclic germylene-borane adduct [L{(Me3Si)2N}Ge→BH3] (3). Following the isolation of 3 to show the basicity of [LGeN(SiMe3)2], NHGe reacted with germanium(II) chloride and tin(II) chloride to yield the N-heterocyclic germylene-dichlorogermylene adduct, [L{(Me3Si)2N}Ge→GeCl2] (4) and the first N-heterocyclic germylene-dichlorostannylene adduct, [L{(Me3Si)2N}Ge→SnCl2] (5), respectively. In contrast, the N-heterocyclic stannylene, [LSnN(SiMe3)2] is unable to coordinate with borane, germanium(II) chloride and tin(II) chloride to form the corresponding adducts. Instead, ligand exchange reactions took place to afford the chlorogermylene [LGeCl] and chlorostannylene [LSnCl] respectively. Compound 3, 4 and 5 were characterized by single crystal X-ray diffraction, NMR spectroscopy, elemental analysis and melting point determination.
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spelling ntu-10356/689702023-02-28T23:43:36Z N-heterocyclic germylene-metal adducts Leong, Bi Xiang So Cheuk Wai School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Inorganic chemistry::Metals The N-heterocyclic chlorogermylene and chlorostannylene of composition [L"E" ̈Cl] (E = Ge, Sn; L = PhC(NtBu)2) is a Lewis bases due to the stabilization of the metal centres’ empty orbitals being stabilized by the lone pair electrons on the nitrogen atom of the ligand. Further stabilization was reinforced by replacing the Cl atom by the bulky and electron-donating bis(trimethylsily)amide substituent to form [L"E" ̈N(SiMe3)2] (E = Ge, Sn). In order to demonstrate the Lewis basicity of these compounds, [LGeN(SiMe3)2] was reacted with Lewis acidic borane to afford the N-heterocyclic germylene-borane adduct [L{(Me3Si)2N}Ge→BH3] (3). Following the isolation of 3 to show the basicity of [LGeN(SiMe3)2], NHGe reacted with germanium(II) chloride and tin(II) chloride to yield the N-heterocyclic germylene-dichlorogermylene adduct, [L{(Me3Si)2N}Ge→GeCl2] (4) and the first N-heterocyclic germylene-dichlorostannylene adduct, [L{(Me3Si)2N}Ge→SnCl2] (5), respectively. In contrast, the N-heterocyclic stannylene, [LSnN(SiMe3)2] is unable to coordinate with borane, germanium(II) chloride and tin(II) chloride to form the corresponding adducts. Instead, ligand exchange reactions took place to afford the chlorogermylene [LGeCl] and chlorostannylene [LSnCl] respectively. Compound 3, 4 and 5 were characterized by single crystal X-ray diffraction, NMR spectroscopy, elemental analysis and melting point determination. ​Master of Science 2016-08-22T01:17:20Z 2016-08-22T01:17:20Z 2016 Thesis http://hdl.handle.net/10356/68970 en 41 p. application/pdf
spellingShingle DRNTU::Science::Chemistry::Inorganic chemistry::Metals
Leong, Bi Xiang
N-heterocyclic germylene-metal adducts
title N-heterocyclic germylene-metal adducts
title_full N-heterocyclic germylene-metal adducts
title_fullStr N-heterocyclic germylene-metal adducts
title_full_unstemmed N-heterocyclic germylene-metal adducts
title_short N-heterocyclic germylene-metal adducts
title_sort n heterocyclic germylene metal adducts
topic DRNTU::Science::Chemistry::Inorganic chemistry::Metals
url http://hdl.handle.net/10356/68970
work_keys_str_mv AT leongbixiang nheterocyclicgermylenemetaladducts