Reactions of the cationic zinc thiolate model complex [Zn(Tab)4](PF6)2 with N-donor ligands and cobalt dichloride.

Reactions of [Zn(Tab)(4)](PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) (1) with 2,2'-bipyridine (2,2'-bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), N-methylimidazole (N-Meim), and 2,6-bis(pyrazol-3-yl)pyridine (bppy) or with CoCl(2)·6H(2)O at the presence of N-donor ligands (2,2'-bipy, phen, 4,4'-dimethyl-2,2'-bipyridine (4,4'-dmbpy), 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy))gave rise to a family of zinc or cobalt thiolate complexes, [Zn(Tab)(2)(L)](PF(6))(2) (2: L = 2,2'-bipy, 3: L = phen, 4: L = 2,9-dmphen), [Zn(Tab)(2)(N-Meim)(2)](PF(6))(2) (5), [Zn(Tab)(2)(bppy)](PF(6))(2) (6), [Co(Tab)(2)(L)(2)](PF(6))(3) (7: L = 2,2'-bipy, 8: L = phen, 9: L = 4,4'-dmbpy), and [Co(Tab)(bdmppy)Cl](PF(6)) (10). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra,(1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray diffraction. The Zn(II) in [Zn(Tab)(2)L(n)](2+)dications of 2-5 is tetrahedrally coordinated by two Tab ligands and one L or two N-Meim ligands. In 6, the Zn(II) has a distorted trigonal-bipyramidal geometry, coordinated by two Tab ligands and one tridentate bppy ligand. The Co(III) in the [Co(Tab)(2)(L)(2)](3+) trications of 7-9 is octahedraly chelated by two bidentate L ligands and two Tab ligands. In 10, the Co(II) adopts a distorted trigonal-bipyramidal geometry, coordinated by one Cl(-), one Tab ligand, and one tridentate bdmppy. In the formation of 2-6, two Tab ligands are removed from the [Zn(Tab)(4)](2+) dication when it is attacked by L ligands, while in the cases of 7-9, the Zn(II) of the [Zn(Tab)(4)](2+) dication was replaced by Co(III) (derived from oxidation of Co(II) by O(2)) followed by the removal of two Tab ligands via L ligands. In the case of 10, the central Zn(II) of the [Zn(Tab)(4)](2+) dication was displaced by Co(II) followed by the removal of three Tab ligands via one Cl(-) and one tridentate bdmppy. These ligand and metal replacement reactions may provide some interesting information on the interactions of the [Zn(S-Cys)(4)](2-) unit of Zn-MTs with N-heterocyclic ligands and toxic metal ions encountered in a natural environment.

Two [Cu2I2]-based coordination polymers of 1,3-bis(pyridin-4-yl)propane.

Solvothermal reactions of Cu(2)(OH)(2)CO(3) with 1,3-bis(pyridin-4-yl)propane (bpp) in the presence of aqueous ammonia in 4-iodotoluene/CH(3)CN or 1,4-diiodobenzene/CH(3)CN afforded two [Cu(2)I(2)]-based coordination polymers, namely catena-poly[[[di-µ-iodido-dicopper(I)]-bis[µ-1,3-bis(pyridin-4-yl)propane-κ(2)N:N']] p-toluidine tetrasolvate], {[Cu(2)I(2)(C(13)H(14)N(2))(2)]·4C(7)H(9)N}(n), (I), and the analogous 1,4-diiodobenzene monosolvate, {[Cu(2)I(2)(C(13)H(14)N(2))(2)]·C(6)H(4)I(2)}(n), (II). The [Cu(2)I(2)] unit of (I) lies on a centre of symmetry at the mid-point of the two I atoms, while that of (II) has a twofold axis running through the I···I line. In (I) and (II), each Cu centre is tetrahedrally coordinated by two µ-I and two N atoms from two different bpp ligands. Each rhomboid [Cu(2)I(2)] unit can be considered as a four-connecting node linked to the symmetry-related [Cu(2)I(2)] units via two pairs of bpp ligands to form a one-dimensional double chain along the c axis. The dimensions of the [Cu(2)I(2)(bpp)(2)](2) rings in (I) and (II) are different, which may be due to the presence of different guest solvent molecules in the structures. In (I), one p-toluidine molecule, derived from an Ullmann coupling reaction of 4-iodotoluene with ammonia, interacts with the [Cu(2)I(2)] cluster fragment through N-H···I hydrogen bonds, while the two p-toluidine molecules interact via N-H···N hydrogen bonds. In (II), two I atoms of each 1,4-diiodobenzene molecule are linked to the I atoms of the [Cu(2)I(2)] fragments from a neighbouring chain via I···I secondary interactions.

Group 12 metal zwitterionic thiolate compounds: preparation and structural characterization.

Reactions of TabHPF(6) (Tab = 4-(trimethylammonio)benzenethiolate) with three equiv. of M(OAc)(2)·2H(2)O (M = Zn, Cd) gave rise to two tetranuclear adamantane-like compounds, [M(4)(µ-Tab)(6)(Tab)(4)](PF(6))(8)·S (·S: M = Zn, S = DMF·4H(2)O; ·S: M = Cd, S = DMF·5H(2)O). The similar reactions of MCl(2) (M = Zn, Cd, Hg) with four equiv. of TabHPF(6) in the presence of Et(3)N afforded three mononuclear compounds [M(Tab)(4)](PF(6))(2)·S (·S: M = Zn, S = 2(H(2)O)(0.5); ·S: M = Cd, S = 2(H(2)O)(0.5); ·S: M = Hg, S = 2DMF). Treatment of the precursor complex or with equimolar MCl(2) and two equiv. of TabHPF(6) and Et(3)N produced one dinuclear compounds [M(µ-Tab)(Tab)(2)](2)(PF(6))(4)·2DMF·2H(2)O (·2DMF·2H(2)O: M = Zn; ·2DMF·2H(2)O: M = Hg) while analogous reactions of with CdCl(2)·2H(2)O gave rise to [Cd(µ-Tab)(2)(Tab)](2)(PF(6))(4)·2DMF (·2DMF). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, (1)H NMR and single-crystal X-ray crystallography. In or , four M(2+) ions and six S atoms of Tab ligands constitute an adamantane-like [M(4)(µ-S)(6)] cage in which each M(2+) ion is tetrahedrally coordinated by one terminal S and three bridged S atoms from four different Tab ligands. In , each M(2+) center of the [M(Tab)(4)](2+) dication is tetrahedrally coordinated by four S atoms of Tab ligand. Two [M(Tab)(2)](2+) dications in or are further bridged by a pair of Tab ligands to form a dimeric [M(µ-Tab)(Tab)(2)](2)(4+) structure. Each dimeric [(Tab)Cd(µ-Tab)(2)Cd(Tab)](4+) unit in is linked to its two neighboring units via two couples of bridging Tab ligands, thereby generating a unique 1D cationic chain. These results may provide useful information on interpreting structural data of MTs containing group 12 metals.

Reactions of a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF6 with various donor ligands: relevance to methylmercury detoxification.

Reaction of MeHgI with Ag(2)O in H(2)O followed by addition of equimolar TabHPF(6) in MeCN gave rise to a methylmercury zwitterionic thiolate complex [MeHg(Tab)]PF(6) (1) (TabH = 4-(trimethylammonio)benzenethiol) in a high yield. Treatment of 1 with KI and KSCN afforded an anion exchange product [MeHg(Tab)]I·0.25H(2)O (2·0.25H(2)O) and [MeHg(Tab)]SCN (3), respectively, while that of 1 with equimolar Tab resulted in the formation of another MeHg/Tab compound [MeHg(Tab)(2)]PF(6) (4). The cation of 2 or 3 shows an approximately linear structure in which the central Hg(II) is coordinated by one C atom of one CH(3) group and one S atom of a Tab ligand. The Hg(ii) center of the cation of 4 is trigonally coordinated by one C atom of the CH(3) group and two S atoms of two Tab ligands. The analogous reaction of 1 with NH(4)SCN led to the cleavage of the Hg-C bond of 1 and the formation of a known four-coordinated Hg(II)/Tab complex [Hg(Tab)(2)(SCN)(2)] (5). When 4 was treated with 4,6-Me(2)pymSH or EtSH, another four-coordinated Hg(II)/Tab complex [Hg(Tab)(4)](3)(PF(6))(6) (6) was generated in a high yield. The Hg(II) center of each cation of 6 is tetrahedrally coordinated by four S atoms of four Tab ligands. The results suggested that cleavage of the Hg-C bond in the methylmercury complex 1 could be completed by increasing the coordination number of its Hg(II) center by S-donor ligands and protonating the methyl group by weak acids.

Reactions of cadmium(II) nitrate with 4-(trimethylammonio)benzenethiolate in the presence of N-donor ligands.

Reactions of Cd(NO(3))(2)·4H(2)O with TabHPF(6) (TabH = 4-(trimethylammonio)benzenethiol) and Et(3)N in the presence of NH(4)SCN and five other N-donor ligands such as 2,2'-bipyridine (2,2'-bipy), phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), 2,6-bis(pyrazd-3-yl)pyridine (bppy) and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy) gave rise to a family of Cd(II)/thiolate complexes of N-donor ligands, {[Cd(2)(µ-Tab)(4)(NCS)(2)](NO(3))(2)·MeOH}(n) (1), [Cd(2)(µ-Tab)(2)(L)(4)](PF(6))(4) (2: L = 2,2'-bipy; 3: L = phen), [Cd(Tab)(2)(L)](PF(6))(2) (4: L = 2,9-dmphen; 5: L = bppy), and [Cd(2)(µ-Tab)(2)(Tab)(2)(bdmppy)](2)(PF(6))(8)·H(2)O (6·H(2)O). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, (1)H NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. For 1, each [Cd(NCS)](+) fragment is connected to its equivalents via a pair of Tab bridges to a one-dimensional chain. For 2 and 3, two [Cd(2,2'-bipy)(2)](2+) or [Cd(phen)(2)](2+) units are linked by a pair of Tab bridges to form a cationic dimeric structure. The Cd atom in [Cd(Tab)(2)(L)](2+) dication of 4 or 5 is coordinated by two Tab ligands and chelated by two N atoms from 2,9-dmphen (4) or three N atoms from bppy (5), forming a distorted tetrahedral (4) or trigonal bipyramidal (5) coordination geometry. For 6, each of two [Cd(Tab)(bdmppy)] fragments is linked to one [(Tab)Cd(µ-Tab)(2)Cd(Tab)] fragment via two Tab bridges to generate a unique cationic zigzag tetrameric structure where the Cd centers take a tetrahedral or a trigonal bipyramidal coordination geometry. The results may provide an interesting insight into mimicking the coordination spheres of the Cd(II) sites of metallothioneins and their interactions with various N-donor ligands encountered in nature.

Mercury(II) thiolate complexes of two flexible benzimidazole-based ligands.

The structure of catena-poly[[{bis[4-(trimethylammonio)benzenethiolate-κS]mercury(II)}-µ-1,1'-(ethane-1,2-diyl)bis(1H-benzimidazole)-κ(2)N(3):N(3')] bis(hexafluoridophosphate) 0.25-hydrate], {[Hg(C(16)H(14)N(4))(C(9)H(13)NS)(2)](PF(6))(2)·0.25H(2)O}(n), contains a one-dimensional zigzag chain. The Hg(II) cation is coordinated by two S atoms of two 4-(trimethylammonio)benzenethiolate (Tab) ligands and by two N atoms from two different 1,1'-(ethane-1,2-diyl)bis(1H-benzimidazole) ligands, forming a distorted seesaw-shaped coordination geometry. The F atoms of the hexafluoridophosphate anion interact with the H atoms of the Tab ligand, generating a two-dimensional network. Furthermore, this layer is connected to neighbouring layers via H···π interactions, thereby forming a three-dimensional hydrogen-bonded structure. In catena-poly[[{[4-(trimethylammonio)benzenethiolate-κS]mercury(II)}bis[µ-4-(trimethylammonio)benzenethiolate-κ(2)S:S]{[4-(trimethylammonio)benzenethiolate-κS]mercury(II)}-µ-1,1'-(hexane-1,6-diyl)bis(1H-benzimidazole)-κ(2)N(3):N(3')] tetrakis(hexafluoridophosphate)], {[Hg(2)(C(20)H(22)N(4))(C(9)H(13)NS)(4)](PF(6))(4)}(n), each Hg(II) cation is coordinated by two S atoms of two Tab ligands and one N atom of the 1,1'-(hexane-1,6-diyl)bis(1H-benzimidazole) (hbbm) ligand, forming a distorted T-shaped coordination geometry, while longer secondary Hg···S bonds join two such units across a centre of inversion to give the tetravalent cation. Adjacent {[Hg(Tab)(2)](2)(µ-hbbm)}(4+) cations are linked through the centrosymmetric hbbm ligands to afford a one-dimensional chain extending along the b axis. Several F atoms interact with the H atoms of the Tab and hbbm ligands, while the S atom interacts with an aromatic H atom of a different Tab ligand, to afford a complex intra- and intermolecular hydrogen-bonding arrangement in a three-dimensional structure.

Bis(acetonitrile-κN)bis[hydridotris(3,5-dimethylpyrazol-1-yl-κN2)borato]di-µ3-sulfido-tetra-µ2-sulfido-di-µ2-thiocyanato-κ2N:S;κ2S:N-tetracopper(I)ditungsten(VI).

Reactions of (Et(4)N)[Tp*WS(3)] [Tp* is hydridotris(3,5-dimethylpyrazol-1-yl)borate] with CuSCN in MeCN in the presence of melamine afforded the title neutral dimeric cluster [Cu(4)W(2)(C(15)H(22)BN(6))(2)(NCS)(2)S(6)(C(2)H(3)N)(2)] or [Tp*W(µ(2)-S)(2)(µ(3)-S)Cu(µ(2)-SCN)(CuMeCN)](2), which has two butterfly-shaped [Tp*WS(3)Cu(2)] cores bridged across a centre of inversion by two (CuSCN)(-) anions. The S atoms of the bridging thiocyanate ligands interact with the H atoms of the methyl groups of the Tp* units of a neighbouring dimer to form a C-H···S hydrogen-bonded chain. The N atoms of the thiocyanate anions interact with the H atoms of the methyl groups of the Tp* units of neighbouring chains, affording a two-dimensional hydrogen-bonded network.

Binding of a coordinatively unsaturated mercury(II) thiolate compound by carboxylate anions.

Reactions of [Hg(Tab)2](PF6)2 (TabH = 4-(trimethylammonio)benzenethiol) (1) with acetic acid (HAc), propanoic acid (HPro), salicylic acid (HSal), benzoic acid (HBez), malonic acid (H2Mal), oxalic acid (H2Oxa), adipic acid (H2Adi), or methylimindiacetic acid (H2Meida) in the presence of Et3N gave rise to a family of mercury(II)-thiolate-carboxylate compounds, [Hg(Tab)2(Ac)](PF6) · 0.5H2O (2 · 0.5H2O), [Hg(Tab)2(Pro)](PF6) (3), [Hg(Tab)2(Sal)](PF6) · MeOH (4 · MeOH), [Hg(Tab)2(Sal)](Sal) · MeOH (5 · MeOH), [Hg(Tab)2(Bez)](PF6) · H2O (6 · H2O), [Hg(Tab)2(HMal)](Mal)0.5 H2O (7 · H2O), [{Hg(Tab)2}2(µ-Oxa)](PF6)2 H2O (8·2H2O), [{Hg(Tab)2}2(µ-Adi)](PF6)2 (9), [Hg(µ-Tab)(µ-Adi)]2n (10), and [Hg(Tab)2(Meida)] · 2.5H2O (11 · 2.5H2O). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. Each mercury(II) atom in [Hg(Tab)2](2+) dication of 2-7 is further coordinated by two oxygen atoms from one Ac(-), Pro(-), Sal(-), Bez(-), Mal(2-) or HMal(-) anion, forming a unique seesaw-shaped coordination geometry. In 8 or 9, two [Hg(Tab)2](2+) dications are connected by one bridging oxalate or adipate dianion to generate a dimeric structure with each mercury(II) center adopting a seesaw-shaped geometry. In 10, a pair of octahedrally coordinated mercury(II) atoms are bridged by two sulfur atoms of two Tab ligands to form a [Hg(µ-Tab)2Hg](4+) fragment, which is further connected to its equivalent ones via four adipate dianions, thereby forming a rare two-dimensional network. In 11, the mercury(II) atom in the [Hg(Tab)2](2+) dication is coordinated by one nitrogen and two oxygen atoms from one Meida(2-) dianion to have a rare square pyramidal geometry. The formation of 2-11 from 1 may be applicable to mimicking the interactions of the mercury(II) sites of Hg-MerR and Hg-MT with various amino acids encountered in nature.

Reactions of a gold(I) thiolate complex [Au(Tab)(2)](2)(PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) with diphosphine ligands.

Reactions of a gold(i) thiolate complex [Au(Tab)(2)](2)(PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) with equimolar 1,2-bis(diphenylphosphine)ethane (dppe), 1,3-bis-(diphenylphosphine)propane (dppp) or 1,4-bis-(diphenylphosphine)butane (dppb) in MeOH-DMF-CH(2)Cl(2) gave rise to three polymeric complexes [Au(2)(Tab)(2)(dppe)](2)(PF(6))(4)·2MeOH (1·2MeOH), [Au(2)(Tab)(2)(dppp)]Cl(2)·0.5MeOH·4H(2)O (2·0.5MeOH·4H(2)O), and [Au(4)(µ-Tab)(2)(Tab)(2)(dppb)](PF(6))(4)·4DMF (3·4DMF), respectively. Analogous reaction of 1 with dppb in DMF/C(2)H(4)Cl(2) produced one tetranuclear complex [Au(2)(µ-Tab)(Tab)(2)](2)Cl(4)·2DMF·4H(2)O (4·2DMF·4H(2)O). Complexes 1-4 were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H and (31)P{(1)H} NMR and single crystal X-ray analysis. Compounds 1 and 2 consist of [Au(Tab)](2) dimeric fragments that are bridged by dppe or dppp ligands to form a 1D linear chain extending along the a axis. For 3, each [Au(4)(Tab)(2)(µ-Tab)(2)] fragment is linked by a pair of dppb ligands to afford another 1D chain extending along the c axis. For 4, the four [Au(Tab)](+) fragments are linked by two Au-Au bonds and two doubly bridging Tab ligands to form a {[Au(Tab)](4)(µ-Tab)(2)} chair-like cyclohexane structure. Hydrogen-bonding interactions in 2 and 4 lead to the formation of interesting 2D hydrogen-bonded networks. The luminescent properties of 1-4 in solid state were also investigated.

Cracking the framework of bulk CuCN with flexible bipyrazolyl-based ligands to assemble [CuCN]n-based coordination polymers.

Solvothermal reactions of CuCN with a set of flexible bipyrazolyl-based ligands with different spacer lengths [(dmpz)(CH(2))(n)(dmpz)] (dmpz = 3,5-dimethyl-pyrazolyl; n = 1-6) gave rise to six [CuCN](n)-based coordination polymers [(CuCN)(3)L](n) (1: L = dmpzm; 2: L = dmpze), [(CuCN)(2)L](n) (3: L = dmpzpr; 4: L = dmpzb; 5: L = dmpzp; 6: L = dmpzh). Compounds 1-6were characterized by elemental analysis, IR, powder X-ray diffraction and single-crystal X-ray diffraction. 1 or 2 exhibits a 1D scolopendra-like chain assembled from a rare 1D zigzag [CuCN](n) chain with [CN-Cu-CN-Cu-L] (1: L = dmpzm; 2: L = dmpze) side arms. 3 or 4 shows a 2D (6,3) wave-like layer in which [Cu(6)(mu-CN)(6)L(2)](n) (L = dmpzpr or dmpzb) double chains are interconnected by pairs of L bridges. 5 consists of two [CuCN](n) single chains that are linked by dmpzp bridges to form a rare 1D chain with an oblong channel. has a 3D network in which the 2D [Cu(10)(mu-CN)(10)(dmpzh)(3)](n) layers are interconnected by pairs of dmpzh bridges. In addition, the photoluminescent properties of 1-6 in the solid state at ambient temperature were investigated.