Tin Organometallic Compounds: Classification and Analysis of Crystallographic and Structural Data: Part Ii. Dimeric Derivatives

Holloway, Clive Ε.; Melnı́k, Milan

doi:10.1515/mgmc.2000.23.6.331

Cited by 15 publications

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“…All the Sn–C distances, averaging 2.1549 Å, are normal . Reported Sn clusters fall into three types as defined by Wiederkehr et al: Zintl clusters derived from Zintl anions, regular clusters with equal numbers of Sn atoms and ligands, and metalloid clusters which contain naked Sn atoms bonded only to other Sn atoms.…”

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Synthesis and Structure of Sn₁₄Cl₆(CH₂SiMe₃)₁₂: Toward Nanoclusters of 4-Coordinate α-Sn

et al. 2018

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Orange crystals of a Sn cluster have been isolated in up to 22% yield from a reaction between MeSiCHSnCl, SnCl, and LiAlH. The structure determined by single crystal X-ray diffraction shows three unique Sn atoms in a 6:6:2 ratio, with all Sn atoms 4-coordinate, similar to the tetrahedral bonding in elemental gray Sn. The solid state Sn MAS NMR spectrum shows the three types of distinct Sn atoms in the expected 3:3:1 intensity ratio with respective chemical shifts of 87.9, -66.6, and -607.1 ppm relative to MeSn. The chemical shift of the two Sn atoms without ligands (bonded only to Sn), at -607.1 ppm, is the most upfield, and is the closest to the chemical shift, reported here, of bulk gray tin (-910 ppm). First-principles density functional theory calculations of the chemical shielding tensors corroborate this assignment. While the core coordination is distorted from the ideal tetrahedral arrangement in the diamond structure of gray tin, this Sn cluster, as the largest reported cluster with all 4-coordinate Sn, represents a major incremental step toward being able to prepare atomically precise nanoparticles of gray tin.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Structure of Sn₁₄Cl₆(CH₂SiMe₃)₁₂: Toward Nanoclusters of 4-Coordinate α-Sn

et al. 2018

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“…Up to the middle of 1997 there have been nearly three thousand structural determinations of tin compounds, including over six hundred coordination derivatives [ 1 ] and almost two thousand organometallic derivatives [2,3,4], While only about eighteen dimeric heterometallic compounds of lead were structurally determined in the same period [5], this review surveys about twenty times as many heterometallic compounds of tin. Up to the middle of 1997 there have been nearly three thousand structural determinations of tin compounds, including over six hundred coordination derivatives [ 1 ] and almost two thousand organometallic derivatives [2,3,4], While only about eighteen dimeric heterometallic compounds of lead were structurally determined in the same period [5], this review surveys about twenty times as many heterometallic compounds of tin.…”

Section: Introductionmentioning

confidence: 99%

Heterometallic Tin Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Dimeric Derivatives

Holloway¹,

Melnı́k²

2001

Main Group Metal Chemistry

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This review covers the crystallographic data for dimeric tin compounds with one other metal atom centre, following the pattern of the previous reviews on tin coordination and organometallic compounds. Over two hundred and forty such derivatives have been characterised, twenty three with a non-transition heterometal atom, one with an actinide metal and the rest with a transition metal atom. The predominant geometries of the tin and the heteroatom are discussed along with the relationships between atom size, bond distances and bond angles. The occurrences of direct metal-metal bonds, and examples of isomerism are illustrated CONTENTS 0. ABBREVIATIONS 1. DIMERIC COMPOUNDS 2.1 Α-Group (Non-Transition) MetalsCrystallographic and structural data for some twenty three tin heterometallic compounds with sub-group A. or non-transition metals, are summarised in Table 1. These are listed in their Periodic Group order, with the typical metals of each group first, and then the Sn-M distance. The first eight derivatives contain tin with lithium [6][7][8][9][10][11][12][13], with the tin in the +2 oxidation state and lithium in its usual +1 oxidation state. The shortest Sn-Li bond 136 Brought to you by | Purdue University Libraries Authenticated Download Date | 6/11/15 11:28 PM Main Group Metal Chemistry Vol. 24, Nr. 3, 2001 distance is found in a yellow derivative [6] at 277.6(4) pm. Here, three Ph(Bu')CN ligands bridge the lithium and tin atoms via their Ν atoms, with Sn-N-Li bridge angles of 81,5( 1A slightly longer Sn-Li distance of 278.4(4) pm is found in a cyclometalated dimer [7] leid together by bridging Ο atoms of three 2,6diphenylphenoxide ligands, with mean Sn-O-Li bridge angles of 84.5(2)°.Two crystallographically independent molecules within the asymmetric units of Ph3SnLi(pmdeta) [8] differ essentially by degree of distortion. While the Sn(II) atom is coordinated by three phenyl groups, the Li(I) atom utilises the tridentate pmdeta moiety. Four coordination is accomplished by each metal via a direct Sn-Li bond of 286.1(7) and 288.2(7) pm in the respective distortion isomers. Another colourless derivative [9] also contains two crystallographically independent molecules. A direct Sn-Li bond of 289(4) and 297(5) pm, respectively, hold together the N3Sn and LiCb moieties.A lithium atom in the next derivative [ 10] ties two amido groups together to generate an N-donor arrangement which forms part of the N3Sn pyramid, one corner of which is the Sn(II) atom. The structure of a red derivative [11] involves a {(Me3Si)3}2Sn unit coordinated to a LiCl(thf)3 moiety via a chlorine bridge. The tricoordinated Sn(II) atom is also at one corner of a pyramid. A tricoordinated tin atom is also found in a metallocyclic arrangement [12] of a four membered (Sn-P-Li-P) ring with average Sn-P-Li angles of 89.5(7)°.The Sn centre in a sandwich style complex [13] is attached to two distorted η-cp ligands and the planar Ν atom of a (Me3Si)2N group, as seen in Figure 1. The tin atom has a distorted pyramidal geometry, and the cp(Y) ligand h...

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Synthesis and Characterization of [Sn8(2,6-Mes2C6H3)4] (Mes=2,4,6-Me3C6H2): A Main Group Metal Cluster with a Unique Structure

Eichler

Power

2001

Angew. Chem.

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Most polyhedral compounds with heavier Group 14 element frameworks fall into one of two broad categories; the Zintl anions E n mÀ , [1] and the substituted species of the formula E n R n , [2] which are accessible through the use of sterically demanding organic (R) groups. Several structural types are known for the latter category [2] which extend from the simplest tetrahedrane cluster E 4 R 4 , through trigonal-prismatic, cubic, and pentagonal-prismatic clusters E 6 R 6 , E 8 R 8 , and E 10 R 10 , respectively. A range [2] of alkyl, aryl, and silyl [3] ligands has been used to stabilize these frameworks. Recently, it has been shown that sterically crowding terphenyl ligands can limit the degree of aggregation in these clusters to n 2 or 3 as in the dimeric alkynelead analogue [Pb 2 (2,6-Trip 2 C 6 H 3 ) 2 ] [4a] (Trip 2,4,6-iPr 3 C 6 H 2 ) or the trimeric germanium radical species [Ge 3 (2,6-Mes 2 C 6 H 3 ) 3 ] [4b] (Mes 2,4,6-Me 3 C 6 H 2 ). The different degrees of aggregation in these two molecules can be rationalized on the basis of the different sizes of germanium and lead as well as the different steric requirements of their terphenyl substituents. These data also suggested that the use of the smaller 2,6-Mes 2 C 6 H 3 aryl ligand in conjunction with tin might result in the isolation of the elusive tetrahedrane cluster Sn 4 R 4 . Herein we show that the attempted preparation of such a species by a coupling reaction of the aryltin halide [{Sn(m-Cl)(2,6-Mes 2 C 6 H 3 )} 2 ] with potassium led not to the expected tetrameric product but to the species [Sn 8 (C 6 H 3 -2,6-Mes 2 ) 4 ] (1), featuring a novel main group element cluster framework which may represent a real structure along the decomposition pathway of Sn n R n clusters toward metallic tin.Compound 1 was synthesized as purple crystals in 38 % yield by reduction of [{Sn(m-Cl)(2,6-Mes 2 C 6 H 3 )} 2 ] [5] with a slight excess of potassium in THF. It was characterized by 1 H, 13 C, and 119 Sn NMR spectroscopy, UV/Vis spectroscopy, and by X-ray crystallography. [6] A thermal ellipsoid drawing (Figure 1) illustrates the crowded environment provided by the ligands. Figure 2 shows that the eight tin atoms of the Sn 8 core are arranged as a distorted rhombic prism with approximate D 2h symmetry. The Sn 8 array may also be thought of as a grossly distorted cubane structure if the long (3.107(2) ) Sn(2)ÀSn(3) and Sn(2A)ÀSn(3A) bonds are uncoupled. It can be seen that only four of the tin atoms carry organic substituents. A similar ratio or organic groups to metal atoms was observed in the cubane cluster [In 8 {2,6-Mes 2 C 6 H 3 } 4 ], [7] but in that compound the four organic groups are attached to alternating corners of an In 8 distorted cubane array with D 2d point symmetry rather than to adjacent metal atoms Figure 1. Structure of 1 (thermal ellipsoid (30 %) plot without H atoms) illustrating the crowding nature of the 2,6-Mes 2 C 6 H 3 substituents.Figure 2. Structure of the core tin and ipso-carbon atoms of 1 (thermal ellipsoid (30 %) plot) showing t...

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Tin Organometallic Compounds: Classification and Analysis of Crystallographic and Structural Data: Part Ii. Dimeric Derivatives

Cited by 15 publications

References 165 publications

Synthesis and Structure of Sn₁₄Cl₆(CH₂SiMe₃)₁₂: Toward Nanoclusters of 4-Coordinate α-Sn

Synthesis and Structure of Sn₁₄Cl₆(CH₂SiMe₃)₁₂: Toward Nanoclusters of 4-Coordinate α-Sn

Heterometallic Tin Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Dimeric Derivatives

Synthesis and Characterization of [Sn8(2,6-Mes2C6H3)4] (Mes=2,4,6-Me3C6H2): A Main Group Metal Cluster with a Unique Structure

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Tin Organometallic Compounds: Classification and Analysis of Crystallographic and Structural Data: Part Ii. Dimeric Derivatives

Cited by 15 publications

References 165 publications

Synthesis and Structure of Sn14Cl6(CH2SiMe3)12: Toward Nanoclusters of 4-Coordinate α-Sn

Synthesis and Structure of Sn14Cl6(CH2SiMe3)12: Toward Nanoclusters of 4-Coordinate α-Sn

Heterometallic Tin Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Dimeric Derivatives

Synthesis and Characterization of [Sn8(2,6-Mes2C6H3)4] (Mes=2,4,6-Me3C6H2): A Main Group Metal Cluster with a Unique Structure

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Synthesis and Structure of Sn₁₄Cl₆(CH₂SiMe₃)₁₂: Toward Nanoclusters of 4-Coordinate α-Sn

Synthesis and Structure of Sn₁₄Cl₆(CH₂SiMe₃)₁₂: Toward Nanoclusters of 4-Coordinate α-Sn