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

Abstract

Monoaryl phosphates with a bulky aryl substituent have been used to synthesize new organotin clusters and polymers. The equimolar reaction between 2,6‐diisopropylphenylphosphate (dipp‐H2) and Me2SnCl2 in ethanol at 25 °C leads to the formation of [Me2Sn(μ3‐dipp)]n (1), while the reaction of 2,6‐dimethylphenylphosphate (dmpp‐H2) with Me2SnCl2 in either a 1:1 or 2:1 molar ratio proceeds to produce exclusively [Me2Sn(μ‐dmpp‐H)2]n·nH2O (2). Compounds 1 and 2 are 1D polymers with different architectures. In compound 1, the tin atom is five‐coordinate (trigonal bipyramidal). Each dipp ligand bridges three different tin atoms to form an infinite ladder‐chain structure. In 2, each six‐coordinate (octahedral) tin atom is surrounded by four phosphate oxygen atoms originating from four different bridging dmpp‐H ligands, thus forming a spirocyclic coordination polymeric chain. The use of nBu2SnO as the diorganotin source in its reaction with dipp‐H2 leads to the isolation of dimeric [nBu2Sn(μ‐dipp‐H)(dipp‐H)]2 (4), which contains a central Sn2O4P2 unit. There are two chemically different half molecules of 4 in the asymmetric part of the unit cell and hence it actually exists as a 1:1 mixture of [nBu2Sn(μ‐dipp‐H)(dipp‐H)]2 and [nBu2Sn(μ‐dipp)(dipp‐H2)]2 in the solid state. The reaction of the monoorgano tin precursor nBuSn(O)(OH)·xH2O with dipp‐H2 takes place in acetone at room temperature to yield the tetrameric cluster 5, which has different structures in the solution and in the solid state. 31P NMR spectroscopy clearly suggests that 5 has the formula [nBu4Sn4(μ‐O)2(μ‐dipp‐H)8] in solution. The single‐crystal X‐ray diffraction studies in the solid state, however, reveal that compound 5 exists as [nBu4Sn4(μ‐OH)2(μ‐dipp‐H)6(μ‐dipp)2]. The use of compounds 1–4 as possible precursors for the preparation of ceramic tin phosphate materials has been investigated. The thermolysis of 1 at 500 °C leads to the formation of quantitative amounts of Sn2P2O7, while the thermolysis of 2, 3, and 4 under similar conditions results in the formation of SnP2O7. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Structural Diversity in Zinc Phosphates and Phosphinates: Observation of a Lattice Water Dimer Sandwiched Between Phosphoryl Oxygen Atoms

“…[10][11][12] In contrast to metal phosphates and phosphonates possessing extended structures, their molecular analogues, at oligonuclear scale, have been receiving attention only in the last decade. [13][14][15][16][17] These limited studies already suggest that the structures of the molecular metal phosphates and phosphonates are dependent on the type of metal precursor used, the substituents on the phosphorus atom, as well as the nature of any co-ligands employed for additional stabilization. It has been shown by Roesky [14b] Reaction of zinc acetate (instead of ZnMe 2 ) with tert-butylphosphonic acid in the presence of 2-aminopyridine results in the isolation of cubane-like zinc phosphonate clusters which are arranged in the lattice as a 3-dimensional supramolecular framework with the aid of noncovalent interactions.…”

Self‐assembly syntheses and crystal structures of dimeric di‐n‐butyltin phosphates containing eight‐membered Sn2O4P2 inorganic ring

“…The bond lengths of Sn1 O1 and Sn1 O5 (for complex 1) are 2.182(2) and 2.200(2)Å, respectively, which are longer than the sum of the covalent radii of the tin and oxygen atoms, both of which are similar to those reported in the literature. The Sn O bond lengths (2.03-2.23Å) of complexes 1 and 2 are similar to the Sn O bond lengths (2.027-2.26Å) of [n-Bu 2 Sn(μ-dipp-H)-(dipp-H)] 2 [22]. The phosphate group (P1) FIGURE 3 Two-dimensional network of complex 1 (the β-, γ-, and δ-carbon atoms of the n -butyl groups on the tin atoms have been omitted for clarity).…”

Organotin Phosphates Assembled from a Sterically Hindered Organophosphate, ArOP(O)(OH)2, (Ar = 2,6-(CHPh2)2-4-i-Pr-C6H2): Syntheses and Structures

“…13 Indeed, previous studies on the reactions of phosphates with organotin substrates, though sparse, have already revealed significant structural variation. 14 Thus, previous work involving the reaction of t-BuP(O)(OH) 2 with benzyl tin derivatives, (PhCH 2 ) 2 SnCl 2 , (PhCH 2 ) 2 SnO•H 2 O, and (PhCH 2 ) 3 SnCl revealed the formation of tetranuclear ensembles such as [(PhCH 2 ) 2 Sn 2 O(O 2 P(OH)-t-Bu) 4 ] 2 (Figure 1a). 15 On the other hand, the reactions of bis(triphenyl)tin oxide with 2,6diisopropylphenylphosphate, (ArO)PO 3 H 2 (Ar = 2,6-i-Pr 2 -C 6 H 3 ), afforded a double-bicapped hexanuclear monoorganooxotin cage (Figure 1b).…”

“…As mentioned above, unlike the reactions of many protic acids with organotin substrates, with phosphates, only two types of structures are known thus far, involving a tetranuclear and a hexanuclear derivative. 14,16 In the current investigation, we were interested if we can isolate other types of compounds if we varied the reaction condition and starting materials. A previous report 14 4).…”