Organotin clusters. 6. Tetranuclear organooxotin cage compounds formed with phosphate and phosphonate ligands. A new class of organotin clusters

Structural Diversity in Organotin Compounds Derived from Bulky Monoaryl Phosphates: Dimeric, Tetrameric, and Polymeric Tin Phosphate Complexes

“…The molecule is centrosymmetric and contains four tin atoms and eight phosphate molecules. The core structure of 5 es-sentially resembles the tert-butylphosphonate tin clusters [(nBuSn) 4 (O) 2 (tbp-H) 8 ] [11] or [(PhCH 2 Sn) 4 (O) 2 (tbp-H) 8 ] [14] ( Figure 8). However, the overall solid-state structure of 5 is clearly different from its solution structure or from the solid-state structures reported for [(nBuSn) 4 (O) 2 (tbp-H) 8 ] [11] or [(PhCH 2 Sn) 4 (O) 2 (tbp-H) 8 ].…”

“…The core structure of 5 es-sentially resembles the tert-butylphosphonate tin clusters [(nBuSn) 4 (O) 2 (tbp-H) 8 ] [11] or [(PhCH 2 Sn) 4 (O) 2 (tbp-H) 8 ] [14] ( Figure 8). However, the overall solid-state structure of 5 is clearly different from its solution structure or from the solid-state structures reported for [(nBuSn) 4 (O) 2 (tbp-H) 8 ] [11] or [(PhCH 2 Sn) 4 (O) 2 (tbp-H) 8 ]. [14] While the phosphonate clusters are built around two RSn-O-SnR units that are held together by eight tbp-H phosphonate ligands, [11,14] this unit in 5 is a RSn-OH-SnR group.…”

“…Multiplets are observed in the appropriate region for the methyl and methylene protons of the n-butyl groups with expected intensities. In the 31 [11] or [(PhCH 2 Sn) 4 (O) 2 (tbp-H) 8 ] [14] (tbp-H 2 = tert-butylphosphonic acid), which suggests that 5 will also have a similar molecular structure. Thus, the observed 31 P NMR spectral pattern of 5 is consistent with the molecular formula [(nBuSn) 4 (O) 2 (dipp-H) 8 ] n , in which four dipp-H ligands are in one environment, while the remaining four dipp-H ligands are in a different environment, at least in solution.…”

“…[6] After a dormant period in between, Chandrasekhar et al [7] and others [8][9][10] showed in recent years that newer and more interesting tin aggregates and polymers could be synthesized by employing a variety of exotic and suitably designed carboxylic acids, phosphinic acids, sulfonic acids, and other acidic proton-containing main group ligands. Thus, while the interaction of both phosphinic [11][12][13] and phosphonic acids [11,[14][15][16][17] with organotin precursors in the assembly of organostannoxane cages has been a subject of intense investigation for sometime now, the use of phosphate esters for this purpose has been limited to a few sporadic reports. [18] Owing to the important role played by bulky substituents in main group chemistry in recent times, 2 ] n ·nH 2 O (3).…”

Two new organotin(IV)-phosphoryl complexes: crystal structure and Hirshfeld surface analysis

“…The Sn centre have been used in preparation of tin complexes, for example compounds with [N] 3 P(O) [11][12][13] [20,21] segments. Moreover, different coordination environments [22,23] and coordination numbers [24,25] at the Sn atom and also coordination modes (monomer [20], dimer [18,26], polymer [27][28][29] and so on [30,31]) and crystal packing diagrams have been found among through the tin-phosphoryl complexes structures deposited in the Cambridge Structural Database (CSD, version 5.35, February 2014 update) [32].…”