Tin-Based Organo-Zintl Ions: Alkylation and Alkenylation of Sn<sub>9</sub><sup>4−</sup>

Chapman, Donald J.; Sevov, Slavi C.

doi:10.1021/ic800383c

Cited by 59 publications

(45 citation statements)

References 50 publications

(82 reference statements)

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“…The -3 charge is typical for monofunctionalized nine-atomic tetrel anions. [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.…”

Section: Introductionsupporting

confidence: 55%

“…[12] The reaction of K 4 Ge 9 and K 4 Sn 9 with Me 3 SiCϵCSiMe 3 in ethylenediamine (en) yielded the structurally characterized mono-vinylated Sn 9 species and bis-vinylated Ge 9 clusters, respectively. [21][22][23] Although the hydrogen transfer to the acetylene In the presence of [18]crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) and K(C 5 H 5 ) crystals containing both cluster species were isolated and structurally characterized as [K( [18] unit during the formation of the bis-vinylated clusters is under discussion, the synthesis in ethylenediamine has been established for several alkynes. [4,5,[21][22][23][24][25][26][27] Recently, mono-and bis-vinylated heteroatomic clusters [(Ge 9-x Sn x )R 9-x ] (x-5)-in which x = 7, 8 and R = CHCH 2 have been described, [24] whereas the existence of mono-vinylated Ge 9 R clusters has been indicated by mass spectroscopy; a structural characterization exists solely for R = (CH 3 )C=CHCH 2 CH 3 and (CH 3 CH 2 )CH=CHCH 3 , respectively.…”

Section: Introductionmentioning

confidence: 99%

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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

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: 55%

Section: Introductionmentioning

confidence: 99%

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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“…beautiful examples can be found in literature, reaching from coupled clusters [5] over alkylated derivatives [6,7] ending at the involvement of transition metals, where the cluster is acting as a ligand (sometimes under rearrangement of the atoms yielding new cluster shapes) [8] and even endohedral metalloids are formed [9,10] (for a recent overview see [1]). The case is different for the lighter homologue silicon, of which a solution chemistry has only been known since 2004 [11][12][13][14] and very few examples of reactions are known up to now.…”

Section: Open Accessmentioning

confidence: 99%

The First Chelate-Free Crystal Structure of a Silicide Transition Metal Complex [K0.28Rb7.72Si9Ni(CO)2]2·16NH3

Gärtner¹,

Hamberger²,

Korber³

2015

Crystals

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Single-crystals X-ray structure analysis of very thermally labile and moisture sensitive ammoniate crystals of [K0.28Rb7.72Si9Ni(CO)2]2·16NH3 show the presence of the very rarely observed nickel-silicide complex [{Ni(CO)2}2(µ-Si9)2] 8− , which was up to now only known in the 18-crown-6 involving solid [Rb@18-crown-6)]2[K@18-crown-6)]2Rb4[{Ni(CO)2}2(µ-Si9)2]·22NH3. This shows that, like already known for the heavier homologues, the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) is no precondition for the stabilization of the silicide cluster anion in solid state and the absence of the alkali metal ligand even allows for the crystallization in the higher symmetric monoclinic space group C2/c compared to the triclinic space group P-1 when 18-crown-6 is present.

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“…[26][27][28][29][30][31][32] In particular, the [ 3À clusters, wherein R is an exo-bonded alkyl or posttransition metal group, have been prepared by nucleophilic substitution reactions. [33][34][35][36][37][38] Unlike the multicenter two-electron bonding within the E 9 clusters, the exo substituents are attached to the clusters through two-center, two-electron bonds. The substituents are known to affect the solubilities [25,35] and dynamic properties of the clusters, [38] but the reactivities of these ions have not been studied in detail.…”

Section: A C H T U N G T R E N N U N G [Ni@ge 9 ] 3à !A C H T U N G Tmentioning

confidence: 99%

Reactions of exo‐Substituted RSn₉³⁻ Clusters with Pd: Endohedral Cluster Formation and Oxidative Insertion

Kocak¹,

Zavalij²,

Eichhorn³

2011

Chemistry A European J

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Pyridine/ethylenediamine solutions of [Sn(9)SnCy(3)](3-) (1) react with [Pd(PPh(3))(4)] to give new clusters [Pd@Sn(9)SnCy(3)](3-) (2) and [Pd@Sn(9)PdSnCy(3)](3-) (3), depending on stoichiometry. These compounds are formed sequentially and are the first transition metal derivates of exo-substituted Zintl clusters. Oxidative insertion of a Pd atom into the Pd@Sn(9)-SnCy(3) bond of 2 to form 3 represents a new reaction type for Zintl cluster compounds. The conversion Sn(9)(4-)→1→2→3 is a rare case in which charge and mass are conserved in a series of Zintl clusters. Complexes 1, 2, and 3 are all highly fluxional in solution. In all three clusters, the nine Sn vertices are in rapid exchange on the NMR timescale. In 1 and 2, the exo-SnCy(3) substituent also scrambles intramolecularly around the outside of the clusters. In 3, the SnCy(3) group remains attached to the vertex Pd atom. The disparate reactions with the other RSn(9)(3-) ions are discussed.

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Tin-Based Organo-Zintl Ions: Alkylation and Alkenylation of Sn₉⁴⁻

Cited by 59 publications

References 50 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

The First Chelate-Free Crystal Structure of a Silicide Transition Metal Complex [K0.28Rb7.72Si9Ni(CO)2]2·16NH3

Reactions of exo‐Substituted RSn₉³⁻ Clusters with Pd: Endohedral Cluster Formation and Oxidative Insertion

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Tin-Based Organo-Zintl Ions: Alkylation and Alkenylation of Sn94−

Cited by 59 publications

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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

The First Chelate-Free Crystal Structure of a Silicide Transition Metal Complex [K0.28Rb7.72Si9Ni(CO)2]2·16NH3

Reactions of exo‐Substituted RSn93− Clusters with Pd: Endohedral Cluster Formation and Oxidative Insertion

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Tin-Based Organo-Zintl Ions: Alkylation and Alkenylation of Sn₉⁴⁻

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

Reactions of exo‐Substituted RSn₉³⁻ Clusters with Pd: Endohedral Cluster Formation and Oxidative Insertion