Synthesis, Characterization, and Structural Studies of Mixed-Ligand Diorganotin Esters, [R₂Sn(OP(O)(OH)Ph)(OS(O)₂R¹)]_n [R = n-Bu, R¹ = Me (1), n-Pr (2); R = Et, R¹ = Me (3)] with 1D and 3D Coordination Polymeric Motifs

Abstract

Mixed-ligand diorganotin esters, [R 2Sn(OP(O)(OH)Ph)(OS(O) 2R (1))] n [R = n-Bu, R (1) = Me ( 1), n-Pr ( 2); R = Et, R (1) = Me ( 3)], have been synthesized by reacting the tin precursors, R 2Sn(OR (1))OS(O) 2R with an equimolar amount of phenylphosphonic acid under mild conditions (room temperature, 6-8 h, CH 2Cl 2). These have been characterized by IR, multinuclear ( (1)H, (13)C{ (1)H}, (31)P, and (119)Sn) NMR, and single crystal X-ray diffraction studies. The asymmetric unit of 1 is comprised of a tetramer with four crystallographically unique tin atoms. The structure reveals a central eight-membered (Sn-O-S-O) 2 cyclic ring with two exocyclic tin atoms, which results from micro 3-binding of the two methanesulfonate groups. The remaining two sulfonates are monodentate and contribute in O...HO(P) hydrogen bonding. The molecular structure is extended into a 3D coordination polymer with the aid of hydrogenphenylphosphonate group on each tin atom, acting in a micro 2-O 2P mode and forms a series of eight-membered (Sn-O-P-O) 2 rings in the structural framework. 2 and 3 are isostructural and represent linear 1D coordination polymers via micro 2-binding mode of both alkanesulfonate and hydrogenphenylphosphonate groups.

Facile Synthesis of Novel Two- And Three-Dimensional Coordination Polymers Containing Dialkyltin Phosphonate-Based Tri/Tetra-Nuclear Clusters with Appended Sulfonate Groups

“…Interestingly, the secondary building units for these self-assemblies are composed of novel tetra-nuclear (for 1 ) and trinuclear (for 2 , 3 ) tin phosphonate clusters which incorporate two alkanesulfonate groups on the tin centers as the side arm functionalities. The striking difference in the structural features of the coordination-driven self-assemblies, 1 − 3 , derived from these clusters in comparison to those reported earlier is illustrative of the potential of this simple methodology for the construction of porous diorganotin-based MOFs, involving phosphonate and sulfonate ligands.…”

“…The genesis of the ladder structural motif can be achieved by condensation of two μ 2 -hydrogenmethylphosphonate bridged dimeric structural units, [Et 2 Sn(OP(O)(OH)Me)(OSO 2 Et)] 2 via the elimination of ethanesulfonic acid (Chart ). The identity of such dimeric structures as the molecular building block for the construction of 1D and 2D coordination polymers has been reported recently . In spite of large pK2 value (8.4) of the dibasic alkylphosphonic acids, the generation of MePO 3 2− dianion from the dimeric structure under mild conditions is facilitated by the ability of ethanesulfonate ligand to act as a leaving group.…”

“…Following the synthetic method reported earlier, the precursor tin complexes, [R 2 Sn(OR 1 )(OSO 2 R 1 )] n (R = Et, R 1 = Et ( 1a ), Me ( 2a ); R = R 1 = Me ( 3a )) have been synthesized from a direct reaction between dialkyltin oxide, R 2 SnO (R = Et, Me) and excess diethyl/dimethyl sulfite in the presence of ethyl iodide/methyl iodide, respectively. The relevant spectroscopic data of these new compounds are summarized in the Experimental Section.…”

“…To our knowledge, the construction of higher dimensionality diorganotin phosphonate-based MOFs has not been realized until our recent reports on the self-assembled coordination polymers, involving mixed-ligand diorganotin derivatives, [ n -Bu 2 Sn(OP(O)(OH)R)(OSO 2 R 1 )] n (R = Me, Ph; R 1 = Me, Et, n -Pr), bearing hydrogenphosphonate and alkanesulfonate groups on the same tin center. The synthetic method relies on the selective reactivity of the -OR group in the tin precursors, [ n -Bu 2 Sn(OR 1 )(OSO 2 R 1 )] n (R 1 = Me, Et, n -Pr), toward phosphonic acids under mild conditions (rt, CH 2 Cl 2 ).…”

Synthesis and Characterization of the Germanium Sulfonate Ge(CH3SO3)2 – a 3D Coordination Network Solid

“…In such compounds the CH 3 SO 3 – group most commonly acts as bridging ligand and exhibits multidentate coordination, which results in the formation of coordination network solids 10,11. Three‐dimensional (3D) networks have been reported for [ n Bu 2 Sn{OP(O)(OH)Ph}(CH 3 SO 3 )] n ,12 two‐dimensional (2D) structures for ( M O 2 )(CH 3 SO 3 ) 2 ( M = Mo, U) 4 and [(Et 2 Sn) 6 (O 3 P t Bu) 4 (CH 3 SO 3 ) 4 · 2H 2 O] n ,13 and one‐dimensional (1D) coordination polymers for [Sr(CH 3 SO 3 ) 2 (H 2 O)] n ,14 [AgL 1–Me (CH 3 SO 3 )] n [L 1–Me = bis(methylthio)methane],15 Pd(CH 3 SO 3 ) 2 5 and (ReO 3 ) (CH 3 SO 3 ) 4. Recently, the syntheses and crystal structures of the low valent group 14 methanesulfonates Pb(CH 3 SO 3 ) 2 and Sn(CH 3 SO 3 ) 2 have been studied by Gagelmann et al16,17 With regard to the title compound Ge(CH 3 SO 3 ) 2 , both need to be addressed in more detail.…”