Some addition reactions of bisgermavinylidene

Leung, Wing‐Por; Kan, Kwok‐Wai; So, Cheuk‐Wai; Mak, Thomas C. W.

doi:10.1002/aoc.1293

Cited by 16 publications

(3 citation statements)

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“…Further searches for Ge(OR) 2 structures (when calixarenes and hydroxyl ligated species were removed due to inherent problems associated with these compounds for materials production) yielded two structure types: (i) monomeric Ge(OR) 2 where OR = OC(Bu t ) 3 , [49] O(CH 2 ) 2 NMe 2 , [63] (2,6-di-R)phenoxy [where R = tert -butyl (DBP), [21] tert -butyl-Me-4 [51] , 2,6- iso -propylphenyl, [43] phenyl (DPP) [45] ], (2,3,5,6-tetra-phenyl)phenoxy [45] , Ge(DPP) 2 (NMe 2 ) 2 [77] and (ii) dinuclear [(OR)Ge(μ-OR)] 2 where OR = mesityloxo (OMes) [45] and 2,6-di- iso -propyl phenoxide (DIP) [45] . Additionally, for Ge(II) siloxides, the heteroligated [(TPS)Ge(μ-OBu t )] 2 [47] and Ge(TPS) 2 {(TMS)N=P(PH) 2 ] 2 (CH 2 )} [64] have been disseminated as well as the Ge(IV) bis -OSiR 3 complex (porph)Ge(TPS) 2 (porph = 5,10,15,20-tetra kis (2-tri- iso -propysilyl)ethynyl) porphyrinato-N,N’,N”,N”’) [78] . We were also interested in the utility of thiolate derivatives as precursors for Ge(0) or single-source precursor for GeS x .…”

Section: Resultsmentioning

confidence: 99%

“…This unusual arrangement for Ge(II) species forces a small out-of-plane twist (4.22°) of the Ge 2 O 2 core. The terminal Ge-O distances of (TPS) 2 Ge{[(TMS)N=P(PH) 2 ] 2 (CH 2 )} 2 [64] , (porph)Ge(TPS) 2 , and [(TPS)Ge(μ-OBu t )] 2 [47] av 1.80, [78] 1.86, [64] and 1.81 [47] Å, respectively are significantly longer in comparison to those noted for 5 (av 1.78 Å). This variation is most likely a reflection of the dinuclear, homoleptic nature of 5 in comparison to the other compounds.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

et al. 2009

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A series of novel germanium(II) precursors was synthesized to initiate an investigation between the precursors’ structures and the morphologies of the resulting nanoparticles. The precursors were synthesized from the reaction of Ge[N(SiMe3)2]2 or [Ge(OBut)2]2 and the appropriate ligand: N,N’-dibenzylethylenediamine (H2-DBED), tert-butanol (H-OBut), 2,6-di-methyl phenol (H-DMP), 2,6-di-phenyl phenol (H-DPP), tert-butyldimethylsilanol (H-DMBS), triphenylsilanol (H-TPS), triphenylsilanethiol (H-TPST), and benzenethiol (H-PS). The products were identified as: [Ge(μc-DBED)]2 (1, μc= bridging chelating), [Ge(μ-DMP)(DMP)]2 (2), Ge(DPP)2 (3), [Ge(μ-OBut)(DMBS)]2, (4), [Ge(μ-DMBS)(DMBS)]2 (5), Ge(TPS)3(H) (6), [Ge(μ-TPST)(TPST)]2 (7), and Ge(PS)4 (8). The Ge(II) metal centers were found to adopt a pyramidal geometry for 1, 2, 4, 5, 7, a bent arrangement for 3, and a tetrahedral coordination for the Ge(IV) species 6 and 8. Using a simple solution precipitation methodology, Ge(0) nanomaterials were isolated as dots and wires for the majority of precursors. Compound 7 led to the isolation of amorphous GexSy. The nanomaterials isolated were characterized by TEM, EDS, and powder XRD. A correlation between the precursor’s arrangement and final observed nanomorphology was proffered as part of the ‘precursor structure affect’ phenomenon.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

et al. 2009

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“…174 Alternatively, it can behave as a germene precursor. 171 The reactivity of the formal C=Ge bond can be highlighted in the [2+2]-cycloaddition, 1,2 addition 175 and [2+3] cycloaddition 176 reactions. Finally, the weak C=Ge pi bond can be used to generate heterobimetallic complexes of Rh, 173 iron and manganese, 176 or even to fully transfer the carbene fragment to Mo, which are both C centered reactions.…”

Section: Reactivitymentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

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This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e. geminal dianions, stabilized by main group elements. Three cases can thus be considered: the gem dilithio derivative, for which the two substituents at C are neutral, the ylidiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications. Reactivity of doubleylides towards organic compounds. 4.4. Coordination chemistry of double ylides to metallic species. 4.4.1. Coordination to Group 2 Metals. 4.4.2. Coordination to Actinides: Uranium Complexes 4.4.3. Coordination to Group 4 Metals: Zirconium Complexes 4.4.4. Coordination to Group 6 Metals: Tungsten Complexes 4.4.5. Coordination to Group 7 Metals: Manganese and Rhenium Complexes 4.4.6. Coordination to Group 8 Metals: Iron Complexes 4.4.7. Coordination to Group 9 Metals: Rhodium and Iridium Complexes 4.4.8. Coordination to Group 10 Metals 4.4.9. Coordination to Group 11 (Coinage) Metals 4.4.10. Coordination to Group 12 Metals 4.5. Reactivity of double ylides towards main group elements. 4.5.1. Group 13 4.5.2. Group 14 4.5.3. Group 15 4.5.4. Group 16 4.5.5. Group 17 4.6. Carbodicarbenes 4.6.1. Synthesis 4.6.2. Reactivity 4.6.3. Coordination chemistry 4.6.4. Reactivity with main group elements 5. Conclusion 6. Acknowledgements 7. References lengths in complexes [(7)Mg(THF)] 2 and [(14)Mg(THF) 3 ] at 2.156(5)Å and 2.113(4)Å resp. are as expectedly significantly shorter than the ones measured in the dimers [(6a)Mg] 2 and [(10)Mg] 2 at 2.225(2)Å (av.) and 2.267(3)Å (av.). Electronic structureThe question of the nature of the bond between the AE metal and C was addressed. Harder et al.performed a DFT study first on models of [(6a)Ca] 2 and [(6f)Ca] where H atoms were considered in place of the real phenyl groups at P and groups (SiMe 3 and Ar resp.) at N. 49 In the case of the monomeric complex [(6f)Ca], the solvent molecules were not taken into account. Not surprising in light of the difference of electronegativity of the elements, the charge at C varied between -1.623 (monomer) and -1.847 (dimer) whereas charge at Ca varied between +1.760 (monomer) and +1.821 (dimer). The Ca-C bond was thus described as highly ionic. The calculations with the full dimeric system were carried out, and a slightly reduced charge was calculated at C (-1.778). The NPA charges were also compared to the ones in neutral 6aH 2 and the [Ca(6aH) 2 ] complex. Expectedly the charge at C goes from -1.079 to -1.409 to -1.778 (in 6aH2, [Ca(6aH) 2 ], [Ca(6a)] 2 resp.). The charge at N also increases (-1.474 to -1.580 to -1.665 resp.) upon deprotonation at C. Conversely, the charge at P varies but to a small extent (+1.747 to +1.727 to +1.7...

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Synthesis of Functionalized Heteroleptic Germylene Alkoxides

et al. 2022

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N-coordinated Ge(II) alkoxides L 1 (tBuO)Ge (1), L 2 (tBuO)Ge ( 2) and [L 2 (OtBu)Ge • BH 3 ] (4) were prepared. Effect of either chelating ligands L 1 and L 2 or Ge!B interaction on strength of the GeÀ OtBu bond was studied by insertion reaction of PhNCO. As a result, the Ge(II) carbamate L 2 {[(tBuO)OC](Ph)N}Ge (3) was isolated. Alcoholysis exchange reactions of 1 and 2 with substituted phenols were studied to find an easy synthetic protocol for a synthesis of functionalized Ge(II) alkoxides. Reactions yielded Ge(II) alkoxides L 1,2 (2-BrÀ C 6 H 4 O)Ge (5 for L 1 , 8 for L 2 ), L 1,2 (2-MeNHÀ C 6 H 4 O)Ge (6 for L 1 , 9 for L 2 ), L 1,2 (2-Ph 2 PÀ C 6 H 4 O)Ge (7 for L 1 , 10 for L 2 ), L 2 (2-Br-3-OHÀ C 6 H 3 O)Ge ( 11) and L 2 (2-NC 5 H 4 O)Ge (12) containing the additional polar groups Y (Y = Br, MeNH, PPh 2 , OH or N). Finally, phosphane decorated Ge(II) alkoxides 7 and 10 were tested as suitable ligands in reactions with (COD)W(CO) 4 and BH 3 . As a consequence, new complexes [(k 2 -7)W(CO) 4 ] (13) and [L 1 (2-Ph 2 P • {BH 3 }-C 6 H 4 O)Ge • {BH 3 }] (14) were isolated. All compounds were characterized by NMR and IR spectroscopy, and compounds 3, 4, 9 and 11 were additionally characterized by X-ray diffraction analysis.

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Some addition reactions of bisgermavinylidene

Abstract: 3). The results suggested that reactive germavinylidene may exist in solution and is capable of forming addition reaction products. The X-ray structures of 2 and 3 were determined.

Cited by 16 publications

References 31 publications

Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

Synthesis and Characterization of Germanium Coordination Compounds for Production of Germanium Nanomaterials

Geminal Dianions Stabilized by Main Group Elements

Synthesis of Functionalized Heteroleptic Germylene Alkoxides

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