Halide-Capped Tellurium-Containing Macrocycles

The reaction of 1,1,2,3,3-pentamethyltrimethylenephosphinic acid (cycPO2H) with bis(p-methoxyphenyl)tellurium dichloride (1) affords a 12-membered macrocycle [((p-MeOC6H4)2Te)2(μ-O)(μ-cycPO2)(μ4-Cl)]2·C6H6 (2) in good yield. The latter reacts with sodium iodide to give [((p-MeOC6H4)2Te)2(μ-O)(μ-cycPO2)(μ4-I)]2·4C6H6 (3). 2 and 3 are isostructural dicationic macrocycles and contain a Te4P2O6 framework. An interesting aspect of both of these structures is that two counter halide atoms are present as capping ligands above and below the macrocyclic plane enabled by Te---X interactions. In contrast to the macrocyclic product obtained with diorganotellurium dihalide the reaction of diphenyltin dichloride with cycPO2H resulted in the formation of an oxygen-capped cluster [(PhSn)3(μ3-O)(μ-cycPO2)3(μ-OH)3][cycPO2]·CH3CN. The latter is formed by a Sn-Ph cleavage reaction

1,1‘-Ferrocenedicarboxylate-Bridged Redox-Active Organotin and -tellurium-Containing 16-Membered Macrocycles: Synthesis, Structure, and Electrochemistry

The reaction of 1,1‘-ferrocenedicarboxylic acid, LH2, with diorganotin halides R2SnCl2 (R = n-Bu and Bn) or Ar2TeCl2 (Ar = 4-OMe-C6H4) in the presence of triethylamine afforded, in nearly quantitative yields, heterobimetallic tetranuclear macrocycles [R2SnL]2 and [Ar2TeL]2. The molecular structures of these compounds have been confirmed by single-crystal X-ray analysis and show that the two main-group metal atoms within each macrocycle are bridged to each other by two ferrocene carboxylate ligands. In the case of the organotin derivatives the ferrocenedicarboxylate ligand acts in an anisobidentate chelating manner, leading to a hexacoordinate tin present in a skewed trapezoidal bipyramid geometry. In contrast, in the tellurium analogue the ferrocenecarboxylate ligand is monodentate, leading to a tetracoordinate tellurium in a seesaw geometry. ESI-MS studies on these macrocylic complexes reveal that they retain their structural integrity in solution. Electrochemcial studies reveal that [n-Bu2SnL]2 and [Ar2TeL]2 show two quasi-reversible oxidation processes. These compounds have low comproportionation constants (Kc) and can be described as being intermediate between noncoupling and weakly coupled systems. [Bn2SnL]2 also shows two oxidation processes. However, in this instance, the second event is irreversible

A Pentahydrated Diorganotin Cation. Cocrystallization of [{<i>n</i>-Bu₂Sn(H₂O)₅}][CF₃SO₃]₂ and [{<i>n</i>-Bu₂Sn(BPDO-II)₂(H₂O)₂}][CF₃SO₃]₂

A 1:2:1 reaction of [n-Bu2SnO]n, trifluoromethanesulfonic acid, and 4,4′-bipyridine N,N-dioxide (BPDO-II) afforded a cocrystal (1·H2O) of the unprecedented pentahydrated diorganotin cation [{n-Bu2Sn(H2O)5}][CF3SO3]2 (1A) and its coordination product [{n-Bu2Sn(BPDO-II)2(H2O)2}][CF3SO3]2 (1B). A variation in crystallization conditions led to the isolation of a coordination polymer, [{n-Bu2Sn(μ-BPDO-II)(H2O)2}{CF3SO3}2]n (2)

In Situ Generated Hydrated Diorganotin Cations as Synthons for Hydrogen-Bonded and Coordination-Driven 1D-, 2D-, and 3D-Assemblies

The reaction of di-n-butyltin oxide with 1,5-naphthalenedisulfonic acid tetrahydrate in a 2:1 ratio afforded [{n-Bu2Sn(μ-OH)}2{μ-1,5-C10H6(SO3)2}]n (1). The latter is a three-dimensional coordination polymer, in a honeycomb architecture, containing [Sn2(μ-OH)2] repeat units that are connected to each other by the bridging coordination action of the disulfonate ligand. Reaction of [n-R2SnO]n (R = n-Bu or Ph) with 1,5-naphthalenedisulfonic acid tetrahydrate in a 1:1 ratio followed by reaction with bifunctional N-oxide ligands (4,4′-bipyridine-N,N′-dioxide (BPDO-II), 1,3-bis(4-pyridyl)propane-N,N′-dioxide (BPDO-III), or P-oxide (1,2-bis(diphenylphosphoryl)ethane (DPPOE)) ligands afforded, depending on the stoichiometry/reaction conditions, various compounds: [{n-Bu2Sn(BPDO-II)2(H2O)2}{1,5-C10H6(SO3)2}] (2); [n-Bu2Sn(μ-BPDO-II)(μ-1,5-C10H6(SO3)2)]n (3); [n-Bu2Sn(μ-DPPOE)(μ-1,5-C10H6(SO3)2)]n (4); [{Ph2Sn(μ-BPDO-II)(H2O)2}{1,5-C10H6(SO3)2}·2H2O]n (5·2H2O); [{n-Bu2Sn(μ-BPDO-III)2}{1,5-C10H6(SO3)2}·5H2O]n (6·5H2O); [{n-Bu2Sn(BPDO-III-H)2}{μ-1,5-C10H6(SO3)2}{1,5-C10H6(SO3)2}]n (7); and [{n-Bu2Sn(DPPOE)2}{μ-1,5-C10H6(SO3)2}2{n-Bu2Sn(CH3OH)(μ-OH)}2·2H2O]n (8·2H2O). On the other hand, the reaction of [n-Bu2SnO]n with 1,5-naphthalenedisulfonic acid tetrahydrate in a 2:1 ratio followed by nicotinic acid N-oxide multifunctional ligand (NO-IV) afforded [(n-Bu2Sn)(μ-1,5-C5H4(NO)(COO))2(μ-1,5-C10H6(SO3)2)(n-Bu2Sn)(H2O)(CH3OH)·CH3OH]n (9·CH3OH) and [(Bu2Sn)(H2O)(μ-1,5-C5H4)(NO)(COO))(μ-1,5-C10H6(SO3)2)1/2]n (10). While 2 is a molecular compound, 3 is a coordination polymer containing both sulfonate and N-oxide bridges. 4 is isostructrual with 3 except that the ligand involved is a bifunctional P-oxide ligand. 5 also is a coordination polymer, although, in this case, only the N-oxide ligands are in the coordination sphere of tin. 6 is a coordination polymer containing interlinked 28-membered macrocycles which are formed as a result of the flexible nature of the BPDO-III ligand. In contrast, in 7 one end of the BPDO-III ligand is protonated and hence does not take any part in coordination to tin. In this case, the coordination polymer is formed by the exclusive coordination action of the disulfonate ligand. Compound 8 reveals it to be a coordination polymer containing alternately [Sn2(μ-OH)2] and a discrete tin unit that are connected by disulfonate ligands. The coordination polymers 9 and 10 are obtained by a variation of crystallization conditions in the three-component reactions using NO-IV as the bridging ligand. While 9 is a neutral porous 2D-coordination polymer consisting of two different types of interconnected diorganotin units, 10 is a nonporous 2D-framework containing only one type of diorganotin unit. Most of the compounds prepared in this study showed good thermal stability, as indicated by their thermogravimetric analyses

A Nonanuclear Organostiboxane Cage

The first example of a nonanuclear organostiboxane cage, [(Ph2Sb)2(PhSb)7(μ-O)11(μ3-O)3(μ-OH)2(μ-cycPO2)2(cycPO2)2(H2O)2]·2CH3CN·H2O, containing Sb(V) has been assembled by a mild hydrolysis and Sb−C bond cleavage reaction of [(Ph3Sb)2(μ-O)(μ-cycPO2)2] (cycPO2 = 1,1,2,3,3-pentamethyltrimethylene phosphinate)

In Situ Generated Hydrated Diorganotin Cations as Synthons for Hydrogen-Bonded and Coordination-Driven 1D-, 2D-, and 3D-Assemblies

The reaction of di-n-butyltin oxide with 1,5-naphthalenedisulfonic acid tetrahydrate in a 2:1 ratio afforded [{n-Bu2Sn(μ-OH)}2{μ-1,5-C10H6(SO3)2}]n (1). The latter is a three-dimensional coordination polymer, in a honeycomb architecture, containing [Sn2(μ-OH)2] repeat units that are connected to each other by the bridging coordination action of the disulfonate ligand. Reaction of [n-R2SnO]n (R = n-Bu or Ph) with 1,5-naphthalenedisulfonic acid tetrahydrate in a 1:1 ratio followed by reaction with bifunctional N-oxide ligands (4,4′-bipyridine-N,N′-dioxide (BPDO-II), 1,3-bis(4-pyridyl)propane-N,N′-dioxide (BPDO-III), or P-oxide (1,2-bis(diphenylphosphoryl)ethane (DPPOE)) ligands afforded, depending on the stoichiometry/reaction conditions, various compounds: [{n-Bu2Sn(BPDO-II)2(H2O)2}{1,5-C10H6(SO3)2}] (2); [n-Bu2Sn(μ-BPDO-II)(μ-1,5-C10H6(SO3)2)]n (3); [n-Bu2Sn(μ-DPPOE)(μ-1,5-C10H6(SO3)2)]n (4); [{Ph2Sn(μ-BPDO-II)(H2O)2}{1,5-C10H6(SO3)2}·2H2O]n (5·2H2O); [{n-Bu2Sn(μ-BPDO-III)2}{1,5-C10H6(SO3)2}·5H2O]n (6·5H2O); [{n-Bu2Sn(BPDO-III-H)2}{μ-1,5-C10H6(SO3)2}{1,5-C10H6(SO3)2}]n (7); and [{n-Bu2Sn(DPPOE)2}{μ-1,5-C10H6(SO3)2}2{n-Bu2Sn(CH3OH)(μ-OH)}2·2H2O]n (8·2H2O). On the other hand, the reaction of [n-Bu2SnO]n with 1,5-naphthalenedisulfonic acid tetrahydrate in a 2:1 ratio followed by nicotinic acid N-oxide multifunctional ligand (NO-IV) afforded [(n-Bu2Sn)(μ-1,5-C5H4(NO)(COO))2(μ-1,5-C10H6(SO3)2)(n-Bu2Sn)(H2O)(CH3OH)·CH3OH]n (9·CH3OH) and [(Bu2Sn)(H2O)(μ-1,5-C5H4)(NO)(COO))(μ-1,5-C10H6(SO3)2)1/2]n (10). While 2 is a molecular compound, 3 is a coordination polymer containing both sulfonate and N-oxide bridges. 4 is isostructrual with 3 except that the ligand involved is a bifunctional P-oxide ligand. 5 also is a coordination polymer, although, in this case, only the N-oxide ligands are in the coordination sphere of tin. 6 is a coordination polymer containing interlinked 28-membered macrocycles which are formed as a result of the flexible nature of the BPDO-III ligand. In contrast, in 7 one end of the BPDO-III ligand is protonated and hence does not take any part in coordination to tin. In this case, the coordination polymer is formed by the exclusive coordination action of the disulfonate ligand. Compound 8 reveals it to be a coordination polymer containing alternately [Sn2(μ-OH)2] and a discrete tin unit that are connected by disulfonate ligands. The coordination polymers 9 and 10 are obtained by a variation of crystallization conditions in the three-component reactions using NO-IV as the bridging ligand. While 9 is a neutral porous 2D-coordination polymer consisting of two different types of interconnected diorganotin units, 10 is a nonporous 2D-framework containing only one type of diorganotin unit. Most of the compounds prepared in this study showed good thermal stability, as indicated by their thermogravimetric analyses

In Situ Generated Hydrated Diorganotin Cations as Synthons for Hydrogen-Bonded and Coordination-Driven 1D-, 2D-, and 3D-Assemblies

The reaction of di-n-butyltin oxide with 1,5-naphthalenedisulfonic acid tetrahydrate in a 2:1 ratio afforded [{n-Bu2Sn(μ-OH)}2{μ-1,5-C10H6(SO3)2}]n (1). The latter is a three-dimensional coordination polymer, in a honeycomb architecture, containing [Sn2(μ-OH)2] repeat units that are connected to each other by the bridging coordination action of the disulfonate ligand. Reaction of [n-R2SnO]n (R = n-Bu or Ph) with 1,5-naphthalenedisulfonic acid tetrahydrate in a 1:1 ratio followed by reaction with bifunctional N-oxide ligands (4,4′-bipyridine-N,N′-dioxide (BPDO-II), 1,3-bis(4-pyridyl)propane-N,N′-dioxide (BPDO-III), or P-oxide (1,2-bis(diphenylphosphoryl)ethane (DPPOE)) ligands afforded, depending on the stoichiometry/reaction conditions, various compounds: [{n-Bu2Sn(BPDO-II)2(H2O)2}{1,5-C10H6(SO3)2}] (2); [n-Bu2Sn(μ-BPDO-II)(μ-1,5-C10H6(SO3)2)]n (3); [n-Bu2Sn(μ-DPPOE)(μ-1,5-C10H6(SO3)2)]n (4); [{Ph2Sn(μ-BPDO-II)(H2O)2}{1,5-C10H6(SO3)2}·2H2O]n (5·2H2O); [{n-Bu2Sn(μ-BPDO-III)2}{1,5-C10H6(SO3)2}·5H2O]n (6·5H2O); [{n-Bu2Sn(BPDO-III-H)2}{μ-1,5-C10H6(SO3)2}{1,5-C10H6(SO3)2}]n (7); and [{n-Bu2Sn(DPPOE)2}{μ-1,5-C10H6(SO3)2}2{n-Bu2Sn(CH3OH)(μ-OH)}2·2H2O]n (8·2H2O). On the other hand, the reaction of [n-Bu2SnO]n with 1,5-naphthalenedisulfonic acid tetrahydrate in a 2:1 ratio followed by nicotinic acid N-oxide multifunctional ligand (NO-IV) afforded [(n-Bu2Sn)(μ-1,5-C5H4(NO)(COO))2(μ-1,5-C10H6(SO3)2)(n-Bu2Sn)(H2O)(CH3OH)·CH3OH]n (9·CH3OH) and [(Bu2Sn)(H2O)(μ-1,5-C5H4)(NO)(COO))(μ-1,5-C10H6(SO3)2)1/2]n (10). While 2 is a molecular compound, 3 is a coordination polymer containing both sulfonate and N-oxide bridges. 4 is isostructrual with 3 except that the ligand involved is a bifunctional P-oxide ligand. 5 also is a coordination polymer, although, in this case, only the N-oxide ligands are in the coordination sphere of tin. 6 is a coordination polymer containing interlinked 28-membered macrocycles which are formed as a result of the flexible nature of the BPDO-III ligand. In contrast, in 7 one end of the BPDO-III ligand is protonated and hence does not take any part in coordination to tin. In this case, the coordination polymer is formed by the exclusive coordination action of the disulfonate ligand. Compound 8 reveals it to be a coordination polymer containing alternately [Sn2(μ-OH)2] and a discrete tin unit that are connected by disulfonate ligands. The coordination polymers 9 and 10 are obtained by a variation of crystallization conditions in the three-component reactions using NO-IV as the bridging ligand. While 9 is a neutral porous 2D-coordination polymer consisting of two different types of interconnected diorganotin units, 10 is a nonporous 2D-framework containing only one type of diorganotin unit. Most of the compounds prepared in this study showed good thermal stability, as indicated by their thermogravimetric analyses

A Pentahydrated Diorganotin Cation. Cocrystallization of [{<i>n</i>-Bu₂Sn(H₂O)₅}][CF₃SO₃]₂ and [{<i>n</i>-Bu₂Sn(BPDO-II)₂(H₂O)₂}][CF₃SO₃]₂

A 1:2:1 reaction of [n-Bu2SnO]n, trifluoromethanesulfonic acid, and 4,4′-bipyridine N,N-dioxide (BPDO-II) afforded a cocrystal (1·H2O) of the unprecedented pentahydrated diorganotin cation [{n-Bu2Sn(H2O)5}][CF3SO3]2 (1A) and its coordination product [{n-Bu2Sn(BPDO-II)2(H2O)2}][CF3SO3]2 (1B). A variation in crystallization conditions led to the isolation of a coordination polymer, [{n-Bu2Sn(μ-BPDO-II)(H2O)2}{CF3SO3}2]n (2)

First Example of a Hydrated Monoorganotin Cation: Synthesis and Structure of [{PhSn(H₂O)₃(μ-OH)}₂][{1,5-C₁₀H₆-(SO₃)₂}₂]

The reaction of Ph2SnO with naphthalene-1,5-disulfonic acid tetrahydrate affords, through a Sn−aryl bond cleavage process, the first example of a hydrated monoorganotin cation, [{PhSn(H2O)3(μ-OH)}2][{1,5-C10H6-(SO3)2}2]. The structural elucidation of the latter showed that it contained a tetracationic dinuclear unit where the two tin atoms are bridged by two hydroxide ligands and each tin is hydrated with three molecules of water. Intermolecular hydrogen-bonding interactions between the water molecules and the disulfonate anions result in a pillared three-dimensional network

Reactions of 3,5-Pyrazoledicarboxylic Acid with Organotin Chlorides and Oxides. Coordination Polymers Containing Organotin Macrocycles

The reaction of 3,5-pyrazoledicarboxylic acid (LH3) with di- and triorganotin substrates has been investigated. The reaction of LH3 with (PhCH2)2SnCl2 afforded a macrocycle-containing coordination polymer [{((PhCH2)2Sn)6(μ-L)4(μ-OH)2}{((PhCH2)2SnCl)2}]n (1), which upon reaction treatment with pyridine (py) in the presence of water yielded a coordination polymer [{((PhCH2)2Sn)6(μ-L)4(μ-OH)2(py)2}{((PhCH2)2Sn)2(μ-O)(μ-OH)}2]n (2). Treatment of 1 with 2,4,6-collidine in the presence of water afforded [{(PhCH2Sn)12(μ-O)14(μ-OH)6}{((PhCH2)2Sn)6(μ-L)4(μ-OH)2}]·2C4H8O·2C2H5OH·2H2O (3). The latter contains a dodecanuclear oxotin cage as a dication and a hexanuclear tin macrocycle as the dianion. O−H ··· O hydrogen-bonding interaction between the cation and the anion leads to the formation of a supramolecular 2D polymer containing large macrocyclic voids. In a slight variation, if the reaction of LH3 is carried out with Me2SnCl2 in the presence of KOH, a heterobimetallic compound [{(K)2(H2O)2(μ-H2O)3(EtOH)2}{((CH3)2Sn)4(μ-L)3(μ-OH)}]n·2H2O (4) is formed. An interesting aspect of the structure of 4 is that the two potassium atoms present in this compound are bridged to each other by three water molecules. 4 is a 2D-coordination polymer, which is taken into a 3D supramolecular structure by solvent ethanol molecules. The reactions of LH3 with Ph2SnO lead to the formation of an insoluble product 5a, which could be dissolved in hot N,N′-dimethylformamide to afford [{(CH3)2NH2}2{(Ph2Sn)(μ-L)(H2O)}2] (5). An analogue of 5, [{(CH3)2NH2}2{(Ph2Sn)(μ-L)(CH3OH)}2] (6), was also prepared more directly by crystallization of 5a in the presence of dimethylamine or bis(dimethylamino)methane. Both 5 and 6 are dinuclear, and their structural integrity is retained in solution as shown by ESI-MS studies. The reaction of (nBu3Sn)2O with LH3 leads to an unusual Sn−alkyl bond cleavage affording a 2D-coordination polymer [(nBu2Sn)2(μ-L)2(nBu3Sn)2]n (8) where dinuclear tin macrocycles are linked to each other by nBu3Sn bridges. In contrast, the reaction of (Ph3Sn)2O with LH3 affords a dinuclear compound [(Ph3Sn)2(μ-LH)(H2O)]·(H2O)2 (9) where the two tin atoms are coordinated by only the carboxylate oxygen atoms. However, the interaction of the coordinated water molecule along with lattice water leads to the formation of a chair-shaped (H2O)6 cluster, which acts as a bridge between two successive molecules