Monoorganotin-polyoxometal-compounds – III. Synthesis and crystal structure of [(ⁿBuSn)₉(V^VO)₃O₁₄(OH)₆Cl₂(dmso)₂] · 3DMSO

Abstract

Organotin compounds / Vanadium / Heteropolyoxometal compounds / Single crystal structure analysis / X-ray diffraction Abstract. The synthesis, molecular and crystal structure of ( n BuSn) 9 (V V O) 3 O 14 (OH) 6 Cl 2 (dmso) 2 Á 3 DMSO (1) are described. The yellow compound crystallizes in the monoclinicThe neutral monoorganotin-polyoxovanadium molecule ( n BuSn) 9 (V V O) 3 O 14 (OH) 6 Cl 2 Â (dmso) 2 (1a) shows the same distorted icosahedral arrangement of the metal atoms and a very similar metal-oxygen framework as the well known [( i PrSn) 12 O 14 (OH) 6 ] 2þ ion (2) from which it can be derived formally by substitution of three square pyramidally coordinated {RSnO 4 } groups by three {OVO 4 } groups of the same geometry. In addition, two further {RSnO 4 } groups are replaced by two octahedral {RSnO 3 Cl(dmso)} units.

Sn12O8(OH)4(OEt)28(HOEt)4: an Additional Member in the Family of Dodecameric Oxo Clusters

“…For example, the metal-oxo framework depicted in Figure 1 is adopted by several members: Ti 12 O 16 (OEt) 16 , 3 {(VO) 12 O 12 F 2 -(OH) 6 } 6-, 4 {(RSn) 12 O 14 (OH) 6 } 2+ (R ) i Pr, Bu, CH 2 SiMe 3 ), 5 and {( i PrSn) 11 Contrary to titanium, for which a unique dodecameric oxo cluster structure has been described (yet with two isomers), 3 tin(IV) contributes more generously to this family. In addition to the monoorganotin oxo clusters with the structure depicted in Figure 1, there are four additional entries: {(BuSn) 9 -(OV) 3 O 14 (OH) 6 Cl 2 (DMSO) 2 }, the oxo framework of which is closely related to the one shown in Figure 1, 7 [Na⊂( i PrSn) 12 O 14 (OH) 24 ] 5+ , which exhibits γ-Keggin's structure and includes a sodium cation at its center, 8 {[Sn(CH 2 ) 3 -Sn] 6 O 10 (OH) 2 (O 2 CCH 2 Cl) 14 }, which consists of bridged stannanes, 9 and {(RSn) 8 O 14 (OH) 8 (SnOH) 4 } (R ) 2,4,6-i Pr 3 C 6 H 2 ), in which the four purely inorganic tin centers are the result of a dearylation process taking place during synthesis. 10 However, despite this diversity, a dodecameric tin oxo cluster without any Sn-C bond is, to the best of our knowledge, neither reported nor mentioned so far in the literature.…”