Redox-active ligands - a viable route to reactive main group metal compounds.

Anionic redox-active ligands such as o-amidophenolates, catecholates, dithiolenes, 1,2-benzendithiolates, 2-amidobenzenethiolates, reduced α-diimines, ferrocenyl and porphyrinates are capable of reversible oxidation and thus have the ability to act as sources of electrons for metal centres. These and other non-innocent ligands have been employed in coordination complexes of base transition metals to influence their redox chemistry and afford compounds with useful catalytic, optical, magnetic and conducting properties. Despite the focus in contemporary main group chemistry on designing reactive compounds with potential catalytic activity, comparatively few studies exploring the chemistry of main group metal complexes incorporating redox-active ligands have been reported. This article highlights relevant chemical reactivity and electrochemical studies that probe the oxidation/reduction of main group metal compounds possessing redox-active ligands and comments on the prospects for this relatively untapped avenue of research.

Synthesis and crystal structure of bis-(µ-2-methyl-benzene-thiol-ato-κ2S:S)bis-[meth-yl(2-methyl-benzene-thiol-ato-κS)indium(III)].

The dinuclear title compound, [In2(CH3)2(C7H7S)4] or [Me(2-MeC6H4S)In-µ-(2-MeC6H4S)2InMe(2-MeC6H4S)], was prepared from the 1:2 reaction of Me3In and 2-MeC6H4SH in toluene. Its crystal structure exhibits a four-membered In2S2 ring core via bridging (2-MeC6H4S) groups. The dimeric units are further associated into a one-dimensional polymeric structure extending parallel to the a axis via inter-molecular In⋯S contacts. The In atoms are then in distorted trigonal-bipyramidal CS4 bonding environments.

Crystal structure of dimethyl-1κ(2) C-bis(µ-4-methylphenolato-1:2κ(2) O:O)(N,N,N',N'-tetramethylethylenediamine-2κ(2) N,N')indium(III)lithium(I).

The mixed bimetallic title compound, [InLi(CH3)2(C7H7O)2(C6H16N2)] or [(tmeda)Li-µ-(4-MeC6H4O)2InMe2] (tmeda is N,N,N',N'-tetra-methyl-ethylenedi-amine), exhibits a four-membered LiO2In ring core via bridging 4-methyl-phenolate groups. The Li and In atoms are in distorted tetra-hedral N2O2 and C2O2 bonding environments, respectively. The Li atom is further chelated by a tmeda group, yielding a spiro-cyclic structure.

Structural variation in ethylenediamine and -diphosphine adducts of (2,6-Me2C6H3S)2Pb: a single crystal X-ray diffraction and 207Pb solid-state NMR spectroscopy study.

Coordination complexes of (2,6-Me2C6H3S)2Pb (1) with flexible bidentate ligands have been prepared to explore new bonding environments for Pb(II) thiolates. The reaction of 1 with a series of ethylenediamine and ethylenediphosphine ligands resulted in isolation of the adducts [(2,6-Me2C6H3S)2Pb]2(tmeda) (9), [(2,6-Me2C6H3S)2Pb]3(dmpe) (10) and [(2,6-Me2C6H3S)2Pb]2(dppe) (11) [tmeda = N,N,N',N'-tetramethylethylenediamine; dmpe = bis(dimethylphosphino)ethane; dppe = bis(diphenylphosphino)ethane]. The X-ray crystal structure of 9 shows a dinuclear species in which tmeda is chelating a ψ-trigonal bipyramidal S2N2 Pb centre via axial and equatorial sites. The structure of 10 displays a trinuclear structural unit in which dmpe is chelating a ψ-trigonal bipyramidal S2P2 Pb centre via equatorial sites. Compounds 9 and 10 also contain a second unique metal centre with ψ-tetrahedral S3Pb bonding motifs. The structure of 11 shows the dppe ligand bridging two Pb ψ-tetrahedral S2P metal bonding environments. Static (207)Pb solid-state NMR (SSNMR) spectra of 9-11 and [Ph4As][(PhS)3Pb] (12) were acquired with cross polarization (CP)-CPMG and frequency swept pulse (WURST)-CPMG pulse sequences, and the efficiencies of these pulse sequences are compared. The (207)Pb SSNMR spectra reveal that the lead chemical shift anisotropies (CSA) vary greatly between the different Pb sites, and are generally large in magnitude. DFT calculations are utilized to relate the orientations of the (207)Pb nuclear magnetic shielding tensors to the molecular structures, and to aid in spectral assignment where multiple Pb centres are present. The combination of X-ray diffraction, (207)Pb SSNMR and DFT is shown to be invaluable for the structural characterization of these important structural motifs, and should find wide-ranging application to numerous lead coordination compounds.

catena-Poly[bis-[dimeth-yl(pyridine-κN)indium(III)]-µ4-benzene-1,3-diolato-bis-[di-methyl-indium(III)]-µ4-benzene-1,3-diolato].

The title compound, [In2(CH3)4(C6H4O2)(C5H5N)] or [{(CH3)2In}(1,3-O2C6H4){In(CH3)2(py)}] n , (py = pyridine) contains two crystallographically unique In(III) ions which are in distorted tetra-hedral C2O2 and distorted trigonal-bipyramidal C2O2N coordination environments. The In(III) coordination centers are bridged head-to-head via In-O bonds, yielding four-membered In2O2 rings and zigzag polymeric chains along [001].

catena-Poly[[bis(pyridine)-lead(II)]bis(µ-penta-fluoro-benzene-thiol-ato)].

The title compound, [Pb(C(6)F(5)S)(2)(C(5)H(5)N)(2)](n), shows the Pb(II) atom in a ψ-trigonal bipyramidal S(2)N(2) bonding environment. Pyridine N atoms occupy axial sites, while thiol-ate S atoms and a stereochemically active lone pair occupy equatorial sites. Very long inter-molecular Pb⋯S inter-actions [3.618 (4) and 3.614 (4) Å] yield a weakly associated one-dimensional polymeric structure extending parallel to [010].

Bis(µ-diethyl-phosphido-κP:P)bis-[bis(2,4,6-trimethyl-phen-yl)indium(III)].

The title compound, [In(2)(C(9)H(11))(4)(C(4)H(10)P)(2)], contains a centrosymmetric In(2)P(2) core with short inter-molecular In-P bonds. This core has acute P-In-P and obtuse In-P-In bond angles compared with other [R(2)InPR'(2)](2) analogues, due to the presence of the bulky aromatic substituents on the In atom and the non-sterically demanding ethyl substituents on the P atom.

Rationalizing oligomerization in dimethylindium(III) chalcogenolates (Me2InER') (E = O, S, Se): a structural and computational study.

The effect on oligomerization of increased steric bulk in dimethylindium(III) chalcogenolates (Me(2)InER') (E = O, S, Se) has been examined. The facile reaction of Me(3)In with a series of phenols, thiophenols and selenophenols afforded the compounds [Me(2)InO(C(6)H(5))](2) (1), [Me(2)InO(2,6-Me(2)C(6)H(3))](2) (2), Me(2)InO(2,4,6-tBu(3)C(6)H(3)) (3), [Me(2)InS(C(6)H(5))](infinity) (4), [Me(2)InS(2,4,6-tBu(3)C(6)H(3))](infinity) (6), [Me(2)InSe(C(6)H(5))](2) (7), [Me(2)InSe(2,4,6-Me(3)C(6)H(3))](infinity) (8) and [Me(2)InSe(2,4,6-tBu(3)C(6)H(3))](infinity) (9). All compounds have been characterized by elemental analysis, melting point, FT-IR, FT-Raman, solution NMR, and X-ray crystallography. The structures of 1-2 are dimeric via short intermolecular In-O interactions, yielding a symmetric In(2)O(2) unit and a distorted tetrahedral C(2)O(2) bonding environment for indium. Increasing steric bulk in 3 results in the isolation of a monomeric species, exhibiting a distorted trigonal planar C(2)O bonding environment for indium. In contrast to 1, the thiolate analogue 4 exhibits a polymeric structure via mu(2)-SPh groups and a distorted tetrahedral C(2)S(2) bonding environment for indium. Increasing steric bulk resulted in the formation of a chain of weakly coordinated monomers via intermolecular In...S interactions in [Me(2)InS(2,4,6-tBu(3)C(6)H(2))](infinity) (6). Although 7 shows a dimeric species similar to 1, the 2,4,6-trimethyl substituted selenolate analogue 8 exhibits a polymeric structure, while the -Se-2,4,6-tBu(3)C(6)H(3) analogue (9) showing a similar structure to 6. Comparison to previously reported structures of diorganoindium chalcogenolates demonstrates the importance of the methyl substituents on indium in facilitating the isolation of higher (non-dimeric) oligomers. Theoretical calculations demonstrate the significance of altering the R and R' groups and E on the degree of oligomerization in [R(2)InER'](n) species.

Probing lead(II) bonding environments in 4-substituted pyridine adducts of (2,6-Me2C6H3S)2Pb: an X-ray structural and solid-state 207Pb NMR study.

The effect of subtle changes in the sigma-electron donor ability of 4-substituted pyridine ligands on the lead(II) coordination environment of (2,6-Me(2)C(6)H(3)S)(2)Pb (1) adducts has been examined. The reaction of 1 with a series of 4-substituted pyridines in toluene or dichloromethane results in the formation of 1:1 complexes [(2,6-Me(2)C(6)H(3)S)(2)Pb(pyCOH)](2) (3), [(2,6-Me(2)C(6)H(3)S)(2)Pb(pyOMe)](2) (4), and (2,6-Me(2)C(6)H(3)S)(2)Pb(pyNMe(2)) (5) (pyCOH = 4-pyridinecarboxaldehyde; pyOMe = 4-methoxypyridine; pyNMe2 = 4-dimethylaminopyridine), all of which have been structurally characterized by X-ray crystallography. The structures of 3 and 4 are dimeric and have psi-trigonal bipyramidal S(3)N bonding environments, with the 4-substituted pyridine nitrogen and bridging sulfur atoms in axial positions and two thiolate sulfur atoms in equatorial sites. Conversely, compound 5 is monomeric and exhibits a psi-trigonal pyramidal S(2)N bonding environment at lead(II). The observed structures may be rationalized in terms of a simple valence bond model and the sigma-electron donor ability of the 4-pyridine ligands as derived from the analysis of proton affinity values. Solid-state (207)Pb NMR experiments are applied in combination with density functional theory (DFT) calculations to provide further insight into the nature of bonding in 4, 5, and (2,6-Me(2)C(6)H(3)S)(2)Pb(py)(2) (2). The lead chemical shielding (CS) tensor parameters of 2, 4, and 5 reveal some of the largest chemical shielding anisotropies (CSA) observed in lead coordination complexes to date. DFT calculations using the Amsterdam Density Functional (ADF) program, which take into account relativistic effects using the zeroth-order regular approximation (ZORA), yield lead CS tensor components and orientations. Paramagnetic contributions to the lead CS tensor from individual pairs of occupied and virtual molecular orbitals (MOs) are examined to gain insight into the origin of the large CSA. The CS tensor is primarily influenced by mixing of the occupied MOs localized on the sulfur and lead atoms with virtual MOs largely comprised of lead 6p orbitals.

Preferred bonding motif for indium aminoethanethiolate complexes: structural characterization of (Me2NCH2CH2S)2InX/SR (X = Cl, I; R = 4-MeC6H4, 4-MeOC6H4).

The metathesis reaction of InCl3 with Me2NCH2CH2SNa or the redox reaction of indium metal with elemental iodine and the disulfide (Me2NCH2CH2S)2 yield the indium bis(thiolate) complexes (Me2NCH2CH2S)2InX [X = Cl (3) and I (4)], respectively. Compounds 3 and 4 may be further reacted with the appropriate sodium thiolate salts to afford the heteroleptic tris(thiolate) complexes (Me2NCH2CH2S)2InSR [R = 4-MeC6H4 (5), 4-MeOC6H4 (6), and Pr (7)]. Reaction of 2,6-Me2C6H3SNa with 4 affords (Me2NCH2CH2S)2InS(2,6-Me2C6H3) (8), while no reaction is observed with 3, suggesting a greater reactivity for 4. All isolated compounds were characterized by elemental analysis, melting point, and Fourier transform IR and 1H and 13C{1H} NMR spectroscopies. X-ray crystallographic analyses of 3-6 show a bicyclic arrangement and a distorted trigonal-bipyramidal geometry for In in all cases. The two sulfur and one halogen (3 and 4) or three sulfur (5 and 6) atoms occupy equatorial positions, while the nitrogen atoms of the chelating (dimethylamino)ethanethiolate ligands occupy the axial positions. The metric parameters of the (Me2NCH2CH2S)2In framework were found to change minimally upon variation of the X/SR ligand, while the solubility of the corresponding compounds in organic solvents varied greatly. 1H NMR studies in D2O showed that 6 and 7 react slowly with an excess of the tripeptide l-glutathione and that the rate of reaction is affected by the pendant thiolate ligand -SR.

Substituent effects on indium-phosphorus bonding in (4-RC6H4S)3In.PR'3 adducts (R = H, Me, F; R' = Et, Cy, Ph): a spectroscopic, structural, and thermal decomposition study.

The tris(arylthiolate)indium(III) complexes (4-RC(6)H(4)S)(3)In [R = H (5), Me (6), F (7)] were prepared from the 2:3 reaction of elemental indium and the corresponding aryl disulfide in methanol. Reaction of 5-7 with 2 equiv of the appropriate triorganylphosphine in benzene or toluene resulted in isolation of the indium-phosphine adduct series (4-RC(6)H(4)S)(3)In.PR'(3) [R = H, R' = Et (5a), Cy (5b), Ph (5c); R = Me, R' = Et (6a), Cy (6b), Ph (6c); R = F, R' = Et (7a), Cy (7b), Ph (7c)]. These compounds were characterized via elemental analysis, FT-IR, FT-Raman, solution (1)H, (13)C{(1)H}, (31)P{(1)H}, and (19)F (7a-c) NMR spectroscopy, and X-ray crystallography (5c, 6a, 6c, and 7a). NMR spectra show retention of the In-P bond in benzene-d(6) solution, with phosphine (31)P{(1)H} signals shifted downfield compared to the uncoordinated ligand. The X-ray structures show monomeric 1:1 adduct complexes in all cases. The In-P bond distance [2.5863(5)-2.6493(12) A] is influenced significantly by the phosphine substituents but is unaffected by the substituted phenylthiolate ligand. Relatively low melting points (88-130 degrees C) are observed for all adducts, while high-temperature thermal decomposition is observed for the indium thiolate reactants 5-7. DSC/TGA and EI-MS data show a two-step thermal decomposition process, involving an initial loss of the phosphine moiety followed by loss of thiolate ligand.

Monomeric, one- and two-dimensional networks incorporating (2,6-Me2C6H3S)2Pb building blocks.

The amine coordination of lead(II) has been examined through the preparation and structural analysis of Lewis base adducts of bis(thiolato)lead(II) complexes. Reaction of Pb(OAc)(2) with 2,6-dimethylbenzenethiol affords (2,6-Me(2)C(6)H(3)S)(2)Pb (6) in high yield. The solubility of 6 in organic solvents allows for the preparation of the 1:2 Lewis acid-base adduct [(2,6-Me(2)C(6)H(3)S)(2)Pb(py)(2)](7), and 1:1 adducts [(2,6-Me(2)C(6)H(3)S)(2)Pb(micro(2)-bipy)](infinity](8) and [(2,6-Me(2)C(6)H(3)S)(2)Pb(micro(2)-pyr)](infinity)(9)(where py = pyridine, bipy = 4,4'-bipyridyl and pyr = pyrazine) from reaction with an excess of the appropriate amine. In contrast to 7, reaction of (C(6)H(5)S)(2)Pb (1) with pyridine afforded the 2:1 adduct [(C(6)H(5)S)(4)Pb(2)(py)](infinity)(10). Compounds were characterized via elemental analysis, FT-IR, solution (1)H and (13)C[(1)H](6) NMR spectroscopy, and X-ray crystallography (7-10). The structures of 7-9 show the thiolate groups occupying two equatorial positions and two amine nitrogen atoms occupying axial coordination sites, yielding distorted see-saw coordination geometries, or distorted trigonal bipyramids if an equatorial lone pair on lead is considered. The absence of intermolecular contacts in 7 and 8 result in monomeric and one-dimensional polymeric structures, respectively. Weak Pb...S intermolecular contacts in 9 result in the formation of a two-dimensional macrostructure. In contrast, the structure of , shows extensive intermolecular Pb...S interactions, resulting in five- and six-coordinate bonding environments for lead(II), and a complex polymeric structure in the solid state. This demonstrates the ability of the 2,6-dimethylphenylthiolate ligand to limit intermolecular lead-sulfur interactions, while allowing the axial coordination of amine Lewis base ligands.

Identification, isolation, and characterization of cysteinate and thiolactate complexes of bismuth.

Although bismuth compounds have been used in medicine for over 200 years, chemical characterization of complexes involving biological molecules is minimal and mechanisms of bioactivity are ill-defined. The thiophilic nature of bismuth implicates sulfur centers as likely sites for interaction, and we have exploited this feature to identify, isolate, and characterize complexes of bismuth with thiolate-carboxylate bifunctional ligands including the amino acid l-cysteine. The solid-state structures of potassium dichloro(thiopropionato)bismuth (K[1d]), dimethylaminoethanethiolato(thiopropionato)bismuth (4), and dinitrato(cysteinato)bismuthphenanthroline [5(phen)] are compared with data from electrospray ionization mass spectrometry (ESI-MS). ESI-MS is applied to reactions of BiCl(3) or Bi(NO(3))(3) with mercaptosuccinic, malic, and succinic acids to illustrate the general observation of 1:1 and 1:2 complexes.

Synthesis and structures of the first bismuth-ester complexes using heterobifunctional thiolate anchored ligands and mass spectrometric identification of ligand-bridged derivatives.

The first systematic series of bismuth complexes involving ester donors, Bi(SCH(2)C(O)OCH(2)CH(3))Cl(2), Bi(SCH(2)C(O)OCH(3))(2)Cl, and Bi(SCH(2)COOCH(3))(3), has been isolated and characterized by spectroscopic (IR, Raman) and X-ray crystallographic data. In addition, these and other species have been identified by electron-impact, electrospray, and atmospheric pressure chemical ionization mass spectometry. The generally applicable synthetic methodology involves the use of heterobifunctional ligands containing a thiolate moiety as an anchor to facilitate coordinate interactions between weak donors (carbonyls) and weak acids (bismuth). The bifunctional nature of the ligands is manifested in both chelating and bridging roles. Important comparisons can be made with the pharmaceutical agent "colloidal bismuth subcitrate" (CBS). The observations allow for a new appreciation of bioactive bismuth compounds, by providing an approach to study the interaction of biorelevant functional groups with bismuth.

Experimental and theoretical investigations of lithium and magnesium derivatives of bis(tert-butylamido)cyclodiphosph(III/V)- and (V/V)azane mono- and ditellurides.

Deprotonation of bis(tert-butylamido)cyclophosph(III/III)azane with organolithium or organomagnesium reagents followed by oxidation with elemental tellurium is a viable approach to the preparation of metal cyclodiphosphazane mono- and ditellurides. The reaction of the cyclodiphosph(III)azane [tBu(H)NP(mu-NtBu)2PN(H)tBu] (1) with elemental tellurium in boiling toluene affords the monotelluride [tBu(H)N(Te)P(mu-NtBu)2PN(H)tBu] (9). A similar reaction involving the magnesium salt Mg[tBuNP(mu-NtBu)2PNtBu](THF)2 (2) also yields a monotelluride Mg[tBuN(Te)P(mu-NtBu)2PNtBu]-(THF)2 (10). By contrast, reaction of the lithium salt Li2[tBuNP(mu-NtBu)2PNtBu](THF)2 (3) with tellurium results in double oxidation and the formation of the ditellurides Li2[tBuN(Te)P(mu-NtBu)2P(Te)NtBu](THF)4 (11) and Li2-[tBuN(Te)P(mu-NtBu)2P(Te)NtBu](tmeda)2 (12). Compounds 9-12 have been characterized by multinuclear (1H, 7Li, 13C, 31P, and 125Te) NMR, while 9, 10, and 12 have also been characterized by X-ray crystallography. The structure of 9 reveals a typical cis/endo, exo arrangement, with no intermolecular contacts to tellurium. The seco-heterocubic structure, observed in 2, is retained in 10, with the ligand chelating magnesium in an N,N',N"-manner. Unique coordination behavior is exhibited by the ditelluride 12, in which the dianionic ligand is attached to the two lithium centers in both Te,Te' and Te,N bonding modes. Multinuclear NMR data are consistent with retention of the solid-state structures of 9-12 in solution at low temperatures. The reactivity of cyclodiphosph(III/III)azanes toward chalcogens is rationalized by using theoretical calculations (semiempirical PM3 level of theory), which show an inverse correlation between the charge at the phosphorus center and the ease of oxidation.

Synthesis and X-ray structures of dilithium complexes of the phosphonate anions [PhP(E)(N(t)Bu)(2)](2-) (E = O, S, Se, Te) and dimethylaluminum derivatives of [PhP(E)(N(t)Bu)(NH(t)Bu)](-) (E = S, Se).

The dilithium salts of the phosphonate dianions [PhP(E)(N(t)Bu)(2)](2-) (E = O, S, Se) are generated by the lithiation of [PhP(E)(NH(t)Bu)(2)] with n-butyllithium. The formation of the corresponding telluride (E = Te) is achieved by oxidation of [Li(2)[PhP(N(t)Bu)(2)]] with tellurium. X-ray structural determinations revealed dimeric structures [Li(THF)(2)[PhP(E)(N(t)Bu)(2)]](2) in which the monomeric units are linked by Li-E bonds. In the case of E = Se or Te, but not for E = S, transannular Li-E interactions are also observed, resulting in a six-rung ladder. By contrast, for E = O, this synthetic approach yields the Li(2)O-templated tetramer [(THF)Li(2)[PhP(O)(N(t)Bu)(2)]](4).Li(2)O in THF or the tetramer [(Et(2)O)(0.5)Li(2)[PhP(O)(N(t)Bu)(2)]](4) in diethyl ether. The reaction of trimethylaluminum with PhP(E)(NH(t)Bu)(2) produces the complexes Me(2)Al[PhP(E)(N(t)Bu)(NH(t)Bu)] (E = S, Se), which were shown by X-ray crystallography to be N,E-chelated monomers.

Redox chemistry of tellurium bis(tert-butylamido)cyclodiphosph(V)azane disulfide and diselenide systems: a spectroscopic and structural study.

The redox chemistry of tellurium-chalcogenide systems is examined via reactions of tellurium(IV) tetrachloride with Li[(t)()BuN(E)P(mu-N(t)Bu)(2)P(E)N(H)(t)Bu] (3a, E = S; 3b, E = Se). Reaction of TeCl(4) with 2 equiv of 3a in THF generates the tellurium(IV) species TeCl(3)[HcddS(2)][H(2)cddS(2)] 4a [cddS(2) = (t)BuN(S)P(mu-N(t)Bu)(2)P(S)N(t)Bu] at short reaction times, while reduction to the tellurium(II) complex TeCl(2)[H(2)cddS(2)](2) 5a is observed at longer reaction times. The analogous reaction of TeCl(4) and 3b yields only the tellurium(II) complex TeCl(2)[H(2)cddSe(2)](2) 5b. The use of 4 equiv of 3a or 3b produces Te[HcddE(2)](2) (6a (E = S) or 6b (E = Se)). NMR and EPR studies of the 5:1 reaction of 3a and TeCl(4) in THF or C(6)D(6) indicate that the formation of the Te(II) complex 6a via decomposition of a Te(IV) precursor occurs via a radical process to generate H(2)cddS(2). Abstraction of hydrogen from THF solvent is proposed to account for the formation of 2a. These results are discussed in the context of known tellurium-sulfur and tellurium-nitrogen redox systems. The X-ray crystal structures of 4a.[C(7)H(8)](0.5), 5a, 5b, 6a.[C(6)H(14)](0.5), and 6b.[C(6)H(14)](0.5) have been determined. The cyclodiphosph(V)azane dichalcogenide ligand chelates the tellurium center in an E,N (E = S, Se) manner in 4a.[C(7)H(8)](0.5), 6a.[C(6)H(14)](0.5), and 6b.[C(6)H(14)](0.5) with long Te-N bond distances in each case. Further, a neutral H(2)cddS(2) ligand weakly coordinates the tellurium center in 4a small middle dot[C(7)H(8)](0.5) via a single chalcogen atom. A similar monodentate interaction of two neutral ligands with a TeCl(2) unit is observed in the case of 5a and 5b, giving a trans square planar arrangement at tellurium.

The Structurally Flexible Bicyclic Bis(2-hydroxyethanethiolato)bismuth(III) Complex: A Model for Asymmetric Monoanionic Chelation of Bismuth(III).

Reaction of Bi(NO(3))(3) with 2-mercaptoethanol gives [Bi(SCH(2)CH(2)OH)(2)][NO(3)], 5(NO(3)), independent of stoichiometry. Other salts or derivatives of 5, 5(Cl) and 5(Br), are readily prepared by anion exchange reactions and can also be obtained by reaction of BiX(3) (X = Cl, Br) with 2-mercaptoethanol. Reaction of Bi(CH(3)COO)(3) with 2-mercaptoethanol gives the conjugate base of 5 which is readily protonated with glacial acetic acid to give the acetate salt 5(CH(3)COO). The compounds have been characterized by IR, Raman, and NMR spectroscopies and APCI mass spectrometry. X-ray crystallographic studies of 5(NO(3)) [crystal data: C(4)H(10)O(5)BiS(2)N.H(2)O, I4(1)/a, a = 20.337(6) Å, b = 20.337(6) Å, c = 11.303(7) Å, Z = 16], 5(Cl) [crystal data: C(4)H(10)O(2)BiS(2)Cl, P2(1)/n, a = 8.653(2) Å, b = 10.618(3) Å, c = 10.564(2) Å, beta = 100.51(2) degrees, Z = 4], and 5(CH(3)COO) [crystal data: C(6)H(13)O(4)BiS(2), P2(1)/c, a = 8.089(2) Å, b = 16.313(3) Å, c = 8.708(2) Å, beta = 98.37(3) degrees, Z = 4] show them to each contain the bicyclic bis(2-hydroxyethanethiolato)bismuth framework 5. The conformational features of 5 are dramatically different in each of the structures, perhaps reflecting the relative donor capabilities of the anions. The observations reveal a substantial thermodynamic preference for the thiolate-alcohol chelate in a 2:1 stoichiometry over other possible structural arrangements, which is interpreted in terms of hard and soft acid-base theory and mediation of the acidity of the bismuth site by the double hydroxyl coordination.