锡化物

锡化物是指含锡阴离子的金属间化合物，在有机化学上也指含有机锡阴离子的化合物。^[1]

碱金属和碱土金属的二元锡化物

当锡和碱金属或碱土金属化合，其中一部分形成离子化合物，含单原子或多原子的锡阴离子（Zintl离子），如Mg₂Sn中的Sn⁴⁻、^[2]K₄Sn₉中的Sn₉⁴⁻等。^[3] 即便是这些金属，并不是所有形成的化合物都可以被认为是具有局部键合的离子的，如金属间化合物Sr₃Sn₅包含着{Sn₅}四方锥单元。^[4]

碱金属和碱土金属的三元锡化物

三元锡化物，如LiRh₃Sn₅^[5]和MgRuSn₄ ^[6]，包含着碱金属（碱土金属）、过渡金属和锡三种元素的化合物也得到了研究。

其它金属的锡化物

二元和三元的金属间锡化物也都是已知的。锡化铌（化学式：Nb₃Sn）是最注明的金属间锡化物超导体，它更常被称作“niobium-tin（铌锡）”。

多锡化物（Snxy−）

一些锡的Zintl离子在下文列出。它们有的含有二中心二电子键(2c-2e)，有的则是缺电子的，其成键有时可用多面体骨架电子对理论（Wade规则）来计算：由每个锡原子贡献的价电子数等于2（不计s电子）。^[7]有一些硅化物和铅化物也有着相似的结构，如四面体的Si₄⁴⁻、链状的(Si²⁻)_n、Pb₄⁴⁻和Pb₉⁴⁻。^[2]^[8]

Sn⁴⁻，存在于Mg₂Sn中。^[2]
Sn₄⁴⁻，四面体，有2c-2e键，存在于CsSn中。^[2]
Sn₄²⁻，四面体，10电子（2n+2）的closo-簇合物。^[9]
(Sn²⁻)_n，有着2c-2e键的zig-zag chain polymeric anion，存在于BaSn中。^[2]
Sn₅²⁻，closo-簇合物，12电子(2n+2)（三角双锥体），存在于(2,2,2-crypt-Na)₂Sn₅中。^[10]
(Sn₈⁴⁻)_n，聚合的2D阴离子，存在于NaSn₂中。^[11]
Sn₉⁴⁻，根据多面体骨架电子对理论，22电子（2n+4）的nido-簇合物(capped square antiprismatic)，存在于金属间化合物K₄Sn₉中；^[3]以扭曲的离子存在于Na₄Sn₉·7en（en＝乙二胺）中。^[12]
Sn₉³⁻，有顺磁性，21电子，closo-簇合物阴离子( D_3h symmetry) (比根据多面体骨架电子对理论预测的20个电子（2n+2）多出了1个）。^[13]
(Sn₁₂⁷⁻)_n，聚合的2D阴离子，存在于Na₇Sn₁₂中。^[14]

参考文献

[1]
Flacke, F.; Jacobs, H. [Li(NH₃)₄] [Sn(SnPh₃)₃].C₆H₆, Crystal structure of a stannide with trigonal pyramidal tin skeleton. European journal of solid state and inorganic chemistry. 1997, 34 (5): 495–501.
[2]
S.M. Kauzlarich,(1994), Zintl Compounds, Encyclopedia of Inorganic Chemistry, John Wiley & sons, ISBN 0-471-93620-0
[3]
Hoch, C.; Wendorff, M.; Röhr, C. Tetrapotassium nonastannide, K₄Sn₉. Acta Crystallogr C. 2002, 58 (4): i45–i46. doi:10.1107/S0108270102002032.
[4]
Klem, M. T.; Vaughey, J. T.; Harp, J G.; Corbett, J D. A3Tt5 Phases Sr₃Sn₅, Ba₃Pb₅, and La₃Sn₅. Structure and Bonding in a Series of Isotypic Metallic Compounds with Increased Electron Count and Their Comparison with the Nominal Zintl Phase La₃In₅. Inorg. Chem. 2001, 40 (27): 7020–7026. doi:10.1021/ic010804v.
[5]
Sreeraj, P; Johrendt, D.; Müller, H.; Hoffmann, R-D; Wu, Zhiyun; Pöttgen, R. The stannide LiRh₃Sn₅ : Synthesis, structure, and chemical bonding. Zeitschrift für Naturforschung B. 2005, 60 (9): 933–939.
[6]
Schlüter, M.; Kunst, A.; Pöttgen, R. The Ternary Stannides MgRuSn₄ and MgxRh₃Sn₇ - x (x = 0.98 - 1.55). Zeitschrift für anorganische und allgemeine Chemie: 2641–2646. doi:10.1002/1521-3749(200211)628:12<2641::AID-ZAAC2641>3.0.CO;2-0.
[7]
Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.
[8]
Yong, Li; Stephan D. Hoffmann; Thomas F. Fässler. A low-dimensional arrangement of [Pb₉]⁴⁻ clusters in [K(18-crown-6)]₂K₂Pb₉·(en)_1.5. Inorganica Chimica Acta (Elsevier). 1 December 2006, 359 (15): 4774–4778. doi:10.1016/j.ica.2006.04.017.
[9]
Critchlow, S C.; Corbett, J. D. Stable homopolyatomic anions: the tetrastannide (2–) and tetragermanide(2–) anions, Sn₄²⁻and Ge₄²⁻ X-ray crystal structure of [K+(crypt)]2Sn₄²⁻. ethylenediamine. J. Chem. Soc., Chem. Commun: 236–237. doi:10.1039/C39810000236.
[10]
Edwards, P. A.; Corbett, J. D. Stable homopolyatomic anions. Synthesis and crystal structures of salts containing the pentaplumbide(2-) and pentastannide(2-) anions. Inorg. Chem. 1977, 16 (4): 903–907. doi:10.1021/ic50170a036.
[11]
Dubois, F.; Schreyer, M.; Fässler, T. F. NaSn₂: A Novel Binary Zintl Phase with 2D Polyanions of Realgar-Type Units [Sn₈]⁴⁻. Inorg. Chem. 2005, 44 (3): 477–479. doi:10.1021/ic048770p.
[12]
Diehl, L.; Khodadadeh, K.; Kummer, D.; Strähle, J. Anorganische Polyederverbindungen, III. Zintl's Polyanionige Salze : Darstellung und Eigenschaften der kristallinen Verbindungen [Na₄·7 en]Sn₉, [Na₄·5 en]Ge₉ und [Na₃·4 en]Sb₇ und ihrer Lösungen Die Kristallstruktur von [Na₄·7 en]Sn₉. Chemische Berichte. 1976, 109 (100): 3404–3418. doi:10.1002/cber.19761091018.
[13]
Critchlow, S. C.; Corbett, J. D. Homopolyatomic anions. The synthesis and characterization of the novel paramagnetic nonastannide(3-) anion Sn₉³⁻, a D_3h cluster with 21 skeletal electrons. J. Am. Chem. Soc. 1983, 105 (17): 5715–5716. doi:10.1021/ja00355a045.
[14]
Fässler, T.F.; Hoffmann, S. Na₇Sn₁₂: A Binary Zintl Phase with a Two-Dimensional Covalently Bonded Tin Framework. Inorg. Chem. 2003, 42 (18): 5474–5476. doi:10.1021/ic030148u.

[1] [1]
Flacke, F.; Jacobs, H. [Li(NH₃)₄] [Sn(SnPh₃)₃].C₆H₆, Crystal structure of a stannide with trigonal pyramidal tin skeleton. European journal of solid state and inorganic chemistry. 1997, 34 (5): 495–501.

[Kauzlarich-2] [2]
S.M. Kauzlarich,(1994), Zintl Compounds, Encyclopedia of Inorganic Chemistry, John Wiley & sons, ISBN 0-471-93620-0

[Hoch-3] [3]
Hoch, C.; Wendorff, M.; Röhr, C. Tetrapotassium nonastannide, K₄Sn₉. Acta Crystallogr C. 2002, 58 (4): i45–i46. doi:10.1107/S0108270102002032.

[4] [4]
Klem, M. T.; Vaughey, J. T.; Harp, J G.; Corbett, J D. A3Tt5 Phases Sr₃Sn₅, Ba₃Pb₅, and La₃Sn₅. Structure and Bonding in a Series of Isotypic Metallic Compounds with Increased Electron Count and Their Comparison with the Nominal Zintl Phase La₃In₅. Inorg. Chem. 2001, 40 (27): 7020–7026. doi:10.1021/ic010804v.

[5] [5]
Sreeraj, P; Johrendt, D.; Müller, H.; Hoffmann, R-D; Wu, Zhiyun; Pöttgen, R. The stannide LiRh₃Sn₅ : Synthesis, structure, and chemical bonding. Zeitschrift für Naturforschung B. 2005, 60 (9): 933–939.

[6] [6]
Schlüter, M.; Kunst, A.; Pöttgen, R. The Ternary Stannides MgRuSn₄ and MgxRh₃Sn₇ - x (x = 0.98 - 1.55). Zeitschrift für anorganische und allgemeine Chemie: 2641–2646. doi:10.1002/1521-3749(200211)628:12<2641::AID-ZAAC2641>3.0.CO;2-0.

[7] [7]
Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.

[8] [8]
Yong, Li; Stephan D. Hoffmann; Thomas F. Fässler. A low-dimensional arrangement of [Pb₉]⁴⁻ clusters in [K(18-crown-6)]₂K₂Pb₉·(en)_1.5. Inorganica Chimica Acta (Elsevier). 1 December 2006, 359 (15): 4774–4778. doi:10.1016/j.ica.2006.04.017.

[9] [9]
Critchlow, S C.; Corbett, J. D. Stable homopolyatomic anions: the tetrastannide (2–) and tetragermanide(2–) anions, Sn₄²⁻and Ge₄²⁻ X-ray crystal structure of [K+(crypt)]2Sn₄²⁻. ethylenediamine. J. Chem. Soc., Chem. Commun: 236–237. doi:10.1039/C39810000236.

[10] [10]
Edwards, P. A.; Corbett, J. D. Stable homopolyatomic anions. Synthesis and crystal structures of salts containing the pentaplumbide(2-) and pentastannide(2-) anions. Inorg. Chem. 1977, 16 (4): 903–907. doi:10.1021/ic50170a036.

[11] [11]
Dubois, F.; Schreyer, M.; Fässler, T. F. NaSn₂: A Novel Binary Zintl Phase with 2D Polyanions of Realgar-Type Units [Sn₈]⁴⁻. Inorg. Chem. 2005, 44 (3): 477–479. doi:10.1021/ic048770p.

[12] [12]
Diehl, L.; Khodadadeh, K.; Kummer, D.; Strähle, J. Anorganische Polyederverbindungen, III. Zintl's Polyanionige Salze : Darstellung und Eigenschaften der kristallinen Verbindungen [Na₄·7 en]Sn₉, [Na₄·5 en]Ge₉ und [Na₃·4 en]Sb₇ und ihrer Lösungen Die Kristallstruktur von [Na₄·7 en]Sn₉. Chemische Berichte. 1976, 109 (100): 3404–3418. doi:10.1002/cber.19761091018.

[13] [13]
Critchlow, S. C.; Corbett, J. D. Homopolyatomic anions. The synthesis and characterization of the novel paramagnetic nonastannide(3-) anion Sn₉³⁻, a D_3h cluster with 21 skeletal electrons. J. Am. Chem. Soc. 1983, 105 (17): 5715–5716. doi:10.1021/ja00355a045.

[14] [14]
Fässler, T.F.; Hoffmann, S. Na₇Sn₁₂: A Binary Zintl Phase with a Two-Dimensional Covalently Bonded Tin Framework. Inorg. Chem. 2003, 42 (18): 5474–5476. doi:10.1021/ic030148u.

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