Heteroatomic Deltahedral Zintl Ions of Group 14 and their Alkenylation

Gillett-Kunnath, Miriam M.; Petrov, I.; Sevov, Slavi C.

doi:10.1021/ic9019487

Cited by 42 publications

(39 citation statements)

References 76 publications

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“…[23,24] The shape of the cluster is very similar to the known analogous clusters functionalized by one or two main-group organometallic fragments or organic groups. [21,22,24,26,27] The mesityl group in 1a is connected to Ge1, which is part of the open square of the cluster. The Ge-C distance of 2.03(1) Å is in agreement with the Ge-C bond length of 1.94(1) Å in [Ph-Ge 9 -SbPh 2 ] 2-.…”

Section: Introductionsupporting

confidence: 53%

Syntheses and ¹H NMR Spectra of Substituted Zintl Ions [Ge₉R_n]^(4–n)–: Crystal Structures of [Ge₉R]^3– (R = 2,4,6‐Me₃C₆H₂, CHCH₂) and Indication of Tris‐Vinylated Clusters

et al. 2011

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The introduction of a mesityl (Mes; 2,4,6‐Me3C6H2) ligand to a Ge9 polyanion is accomplished by the reaction of [Ge9]4– solutions with Ag4Mes4. The crystal structure investigation of its [K([2.2.2]crypt)] salt ([2.2.2]crypt: 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) shows that [Ge9Mes]3– comprises one exo‐bonded aryl ligand in accordance with the 1H NMR spectroscopic data. The formation of mono‐, bis‐, and tris‐substituted Zintl Ions [Ge9Rn](4–n)– (n = 1, 2, and 3; R = CHCH2) is investigated by 1H NMR spectroscopy. The mono‐ and bis‐vinylated Ge9 clusters, [Ge9(CHCH2)]3– and [Ge9(CHCH2)2]2–, were obtained by the reaction of K4Ge9 with Me3SiC≡CSiMe3 in ethylenediamine. In the presence of [18]crown‐6 (1,4,7,10,13,16‐hexaoxacyclooctadecane) and K(C5H5) crystals containing both cluster species were isolated and structurally characterized as[K([18]crown‐6)]2{(η5‐C5H5)[K([18]crown‐6)]2}[Ge9(CHCH2)]and [K([18]crown‐6)]{(η5‐C5H5)[K([18]crown‐6)]2}[Ge9(CHCH2)2], respectively. 1H NMR experiments hint for the tris‐vinylated cluster [Ge9(CHCH2)3]–.

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Section: Introductionsupporting

confidence: 53%

Syntheses and ¹H NMR Spectra of Substituted Zintl Ions [Ge₉R_n]^(4–n)–: Crystal Structures of [Ge₉R]^3– (R = 2,4,6‐Me₃C₆H₂, CHCH₂) and Indication of Tris‐Vinylated Clusters

et al. 2011

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“…To examine the stability of the Ge-C core, crystals of 1 were dissolved in a solution of DMF, and ESMS clearly showed that the sp 3 hybridized carbon cluster core remained intact even after ionization (see Figure 2). In the positive ion mode, several cluster species were characterized by their isotope pattern [18,19,34,41,42]. The clusters retained the mass of the core Ge4C with several halides (m/z = CCl11Ge4 + (691), CBrCl10Ge4 + (737), CBr2Cl9Ge4 + (781), CBr3Cl8Ge4 + (825), and CBr4Cl7Ge4 + (870)), thus supporting the stability of compound 1.…”

Section: Synthesis Results and Discussionmentioning

confidence: 82%

“…The clusters retained the mass of the core Ge4C with several halides (m/z = CCl11Ge4 + (691), CBrCl10Ge4 + (737), CBr2Cl9Ge4 + (781), CBr3Cl8Ge4 + (825), and CBr4Cl7Ge4 + (870)), thus supporting the stability of compound 1. Such multi metal-chalcogenide clusters, with partial oxidation caused by the electric ESMS field, is a common phenomenon when being ionized [41,42]. However, evidence of the intact core was unexpected as the Ge-Cl (356 kJ/mol) and Ge-Br (276 kJ/mol) have stronger bond dissociation energies than the Ge-C (255 kJ/mol) bond.…”

Section: Synthesis Results and Discussionmentioning

confidence: 99%

Gas Source Techniques for Molecular Beam Epitaxy of Highly Mismatched Ge Alloys

et al. 2016

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Ge and its alloys are attractive candidates for a laser compatible with silicon integrated circuits. Dilute germanium carbide (Ge 1−x C x ) offers a particularly interesting prospect. By using a precursor gas with a Ge 4 C core, C can be preferentially incorporated in substitutional sites, suppressing interstitial and C cluster defects. We present a method of reproducible and upscalable gas synthesis of tetrakis(germyl)methane, or (H 3 Ge) 4 C, followed by the design of a hybrid gas/ solid-source molecular beam epitaxy system and subsequent growth of defect-free Ge 1−x C x by molecular beam epitaxy (MBE). Secondary ion mass spectroscopy, transmission electron microscopy and contactless electroreflectance confirm the presence of carbon with very high crystal quality resulting in a decrease in the direct bandgap energy. This technique has broad applicability to growth of highly mismatched alloys by MBE.

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“…We have shown before that the alkenylation of Ge9 clusters by a reaction with alkynes is a nucleophilic addition of the clusters to the triple bond: 55,57 K4Ge9 + 2TMS-C≡C-TMS + 6H2NR → [K]2[Ge9-(CH=CH2)2] + 4TMS-NHR + 2K-NHR where H2NR represents the solvent ethylenediamine. In the reaction, one of the germanium lone pairs attacks the empty π* orbitals of the triple bond and supplies a pair of electrons to it.…”

Section: Running Es-ms Of Reaction Solutionmentioning

confidence: 99%

“…[3][4][5][6] Notable milestones are the oxidative coupling of Ge9 4-clusters to oligomers and infinite chains, 7-19 their metallation, [14][15][16][20][21][22][23][24][25] capping by transition-metal organometallic fragments, 26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization, 35-47 addition of main-group organometallic fragments as exo-bonded substituents, 48-50 and functionalization with various organic residues by reactions with organic halides and alkynes. [51][52][53][54][55][56][57][58] This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge9 4-clusters are extracted later in solution.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

Gillett-Kunnath

Sevov

2012

JoVE

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Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later. 1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9 n-(E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry. [3][4][5][6] Notable milestones are the oxidative coupling of Ge9 4-clusters to oligomers and infinite chains, 7-19 their metallation, [14][15][16][20][21][22][23][24][25] capping by transition-metal organometallic fragments, 26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization, 35-47 addition of main-group organometallic fragments as exo-bonded substituents, 48-50 and functionalization with various organic residues by reactions with organic halides and alkynes. [51][52][53][54][55][56][57][58] This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge9 4-clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2] 2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left undisturbed for a few days, the so-layered solutions produced orange crystalline blocks of [K(18-crown-6)]2[Ge9(HCCH2)2]•en which were characterized by single-crystal X-ray diffraction.The process highlights standard reaction techniques, work-up, and analysis towards functionalized deltahedral Zintl clusters. It is hoped that it will help towards further development and understanding of these compounds in the community at large.

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Heteroatomic Deltahedral Zintl Ions of Group 14 and their Alkenylation

Cited by 42 publications

References 76 publications

Syntheses and ¹H NMR Spectra of Substituted Zintl Ions [Ge₉R_n]^(4–n)–: Crystal Structures of [Ge₉R]^3– (R = 2,4,6‐Me₃C₆H₂, CHCH₂) and Indication of Tris‐Vinylated Clusters

Syntheses and ¹H NMR Spectra of Substituted Zintl Ions [Ge₉R_n]^(4–n)–: Crystal Structures of [Ge₉R]^3– (R = 2,4,6‐Me₃C₆H₂, CHCH₂) and Indication of Tris‐Vinylated Clusters

Gas Source Techniques for Molecular Beam Epitaxy of Highly Mismatched Ge Alloys

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

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Heteroatomic Deltahedral Zintl Ions of Group 14 and their Alkenylation

Cited by 42 publications

References 76 publications

Syntheses and 1H NMR Spectra of Substituted Zintl Ions [Ge9Rn](4–n)–: Crystal Structures of [Ge9R]3– (R = 2,4,6‐Me3C6H2, CHCH2) and Indication of Tris‐Vinylated Clusters

Syntheses and 1H NMR Spectra of Substituted Zintl Ions [Ge9Rn](4–n)–: Crystal Structures of [Ge9R]3– (R = 2,4,6‐Me3C6H2, CHCH2) and Indication of Tris‐Vinylated Clusters

Gas Source Techniques for Molecular Beam Epitaxy of Highly Mismatched Ge Alloys

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

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Syntheses and ¹H NMR Spectra of Substituted Zintl Ions [Ge₉R_n]^(4–n)–: Crystal Structures of [Ge₉R]^3– (R = 2,4,6‐Me₃C₆H₂, CHCH₂) and Indication of Tris‐Vinylated Clusters

Syntheses and ¹H NMR Spectra of Substituted Zintl Ions [Ge₉R_n]^(4–n)–: Crystal Structures of [Ge₉R]^3– (R = 2,4,6‐Me₃C₆H₂, CHCH₂) and Indication of Tris‐Vinylated Clusters