Syntheses And Structures Of Organotin Arsonate Compounds

In the first chapter, the syntheses, the structures and application of organotin oxo clustersare concisely introduced. At the end of this chapter, we pointed out the importance of thesearch project and summarized the important results obtained in the thesis.In the second chapter, reactions of Ph₃SnOH or Ph₃SnCl with the arylarsonic acids give18 Sn-O cluster compounds. These compounds can be classified into four types: type A:[(PhSn)₃(RAsO₃)₃(μ₃-O)(OH)(R'O)₂]₂Sn; type B: [(PhSn)₃(RAsO₃)₂(RAsO₃H)(μ₃-O)(R'O)₂]₂;type C: [(PhSn)₃(RAsO₃)₃(μ₃-O)(R'O)₃]₂Sn; type D: [Sn₃Cl₃(μ₃-O)(R'O)₃]₂(RAsO₃)₄. Thestructures of A and B contain [Sn₃(μ₃-O)(μ₂-OR')₂] building block, while in C and D, thestannoxane cores are built by utilizing two [Sn₃(μ₃-O)(μ₂-OR')₃] building block. Thesyntheses, structures, and structural interrelationship of these diverse organostannoxanecompounds are discussed.In the third chapter, reactions of Ph₃SnCl or Ph₃SnOH with the alkylarsonic acids haveled to seven organotin arsonate clusters: [Sn₃Cl₃(μ₃-O)(R'O)₃]₂(RAsO₃)₄ [R=n-Bu, R'=Et(3-1); R=n-Pr, R'=Et(3-2); R=Bz, R'=Et (3-3); R=n-Pr, R'= Me (3-4) and R =4-NO₂-Bz, R' = Et (3-5)] and [(PhSn)₃(RAsO₃)₃(μ₃-O)(OH)(R'O)₂]₂Sn [R = n-Pr, R' = Et(3-6) and R = 4-NO₂-Bz, R' = Et (3-7)]. Two types of structural units, [Sn₃(μ₃-O)(μ₂-OR')₃]for compounds (3-1)-(3-5) and [Sn₃(μ₃-O)(μ₂-OR')₂] for compounds (3-6) and (3-7), wereobtained by subtle changes of the organotin precursors. For the first time, hydrogen-bondinginteractions such as C-H…Cl, C-H…O and C-H…πwere investigated in the crystal structures oftin alkylarsonate clusters (3-2)-(3-7).In the fourth chapter, treatment of the acetate drum, [n-BuSn(O)O₂CMe]₆, with differentarsonic acids gave seven organotin arsonate clusters: [(n-BuSn)₅(μ₃-O)(OH)(R'O)₃(RAsO₃)₄(RAsO₃H)] [R = 2-NO₂-C₆H₄, R' = Me (4-1a and 4-1b)],[(n-BuSn)₃(RAsO₃)(μ₃-O)(CH₃CO₂)₃(R'O)₂]₂ [R = 2,4-CNO₂)₂-C₆H₃, R' = Me (4-2)],[(n-BuSn)₃(RAsO₃)₂(RAsO₃H)(μ₃-O)(R'O)₂]₂ [R = 4-NO₂-C₆H₄, R' = Me (4-3)] and[(n-BuSn)₃(RAsO₃)₃(μ₃-O)(OH)(R'O)₂]₂Sn [R = C₆H₅CH₂, R' = Me (4-4), C₆H₅CH₂, R' = H(4-5) and C₆H₅, R' = H (4-6)]. The pentanuclear motif of (4-1a) and (4-1a), was firstly foundin organotin compounds. However, the structures of (4-2) and (4-3) present examples ofhexanuclear organotin-oxygen clusters. The heptanuclear structures of (4-4)-(4-6) arecomposed of two [Sn₃(μ₃-O)(μ₂-OR')₂] units connected via hydroxyl and arsonate ligands to asingle tin. The results reveal that the employment of the organotin precursors in syntheses oforganotin-oxygen arsonate clusters is very effective.In the fifth chapter, the polymeric organotin arsonates [n-Bu₂Sn(4-OH-3-NO₂-C₆H₃AsO₃)]_n (5-1) and[n-Bu₂Sn(4-Me-C₆H₄SO₃)(4-NO₂-C₆H₄AsO₃H)]_n (5-2) have been successfully isolated.The sixth chapter is the conclusions.