Synthesis and vibrational spectra of[RSHgII]2+(ClO4)2 complexes. Crystal and molecular structure of bis(N-methylpiperidinium-4-thiolato)-mercury(II) perchlorate.

Barrera, H.; Bayón, J. Carles; González-Duarte, Pilar; Sola, Joan; Viñas, X.; Briansó, J. L.; Brianso, M. C.; Soláns, Xavier

doi:10.1016/s0277-5387(00)80862-1

Cited by 36 publications

(9 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…With the additional secondary bonding between mercury and the oxygen atom of the ether, the mercury(II) atom has a effective coordination number of 5 or 6, resulting in a strongly distorted pentagonal or octahedral geometry around mercury(II). Similar complexes having secondary bonding interactions have been reported, e.g., 3.08(2) Å for the Hg−O distance of [Hg(SC 5 H 9 NH(CH 3 )) 2 ][ClO 4 ] 2 and 2.722(6), 2.826(6), and 3.189(6) Å for bis[2,6-bis(pivaloylamino)benzenethiolato]mercury …”

Section: Resultssupporting

confidence: 77%

Symmetrization of Phenylmercuric Hydroxides by the Action of Nickel(II) and Cobalt(II) Acetylacetonates. Isolation and Structural Characterization of an Intermediate in This Reaction

Döring¹,

Hahn²,

Stoll³

et al. 1997

Organometallics

View full text Add to dashboard Cite

The complex adducts [M(acac)2(PhHgOHgPh)]2 (M = Co, Ni) have been obtained by incorporation of PhHgOH into the coordination sphere of M(acac)2 at ambient temperature. The X-ray crystal structure of [Ni(acac)2(PhHgOHgPh)(Et2O)]2 (1c) reveals a dimeric nickel complex coordinated by the acetylacetonate oxygen and the bridging oxygen of bis(phenylmercuric) oxide. Refluxing a THF solution of compound 1c gave diphenylmercury, HgO, and Ni(acac)2(THF)2. With PhHgOH or PhHgSH the symmetrization reactions also occurred when catalytic amounts of Ni(acac)2 were used. In contrast, triphenyltin derivatives (hydroxide, acetate, oxide) on treatment with M(acac)2 in aqueous THF gave the stable complexes [M(acac)2(Ph3SnOH)]2 (M = Co, Ni). The structure of [Ni(acac)2(Ph3SnOH)]2 (2) was also determined by X-ray crystallography.

show abstract

Section: Resultssupporting

confidence: 77%

Symmetrization of Phenylmercuric Hydroxides by the Action of Nickel(II) and Cobalt(II) Acetylacetonates. Isolation and Structural Characterization of an Intermediate in This Reaction

Döring¹,

Hahn²,

Stoll³

et al. 1997

Organometallics

View full text Add to dashboard Cite

show abstract

“…Actually, most of the reported mononuclear Hg(SR) 2 complexes possess narrow C−S−(Hg)−S−C angles near 120°, e.g. [Hg(SC 5 H 9 NH(CH 3 ) 2 ](ClO 4 ) 2 and [Hg(S- o -SiMe 3 C 6 H 4 ) 2 ], , although a large C−S−(Hg)−S−C torsion angle near 180° was reported for Hg(SEt) 2 , having an intermolecular Hg---S contact 3 H−S−(Hg)−S−H torsion angle dependence of the HOMO in Hg(SH) 2 obtained using EHMO calculations. …”

Section: Resultsmentioning

confidence: 99%

Effect of the NH---S Hydrogen Bond on the Nature of Hg−S Bonding in Bis[2-(acylamino)benzenethiolato]mercury(II) and Bis[2,6-bis(acylamino)benzenethiolato]mercury(II) Complexes

et al. 1996

View full text Add to dashboard Cite

2-(Acylamino)benzenethiolate complexes of Hg(II) having an intramolecular NH---S hydrogen bond, Hg[2-(pivaloylamino)benzenethiolato] 2 and Hg[2,6-bis(pivaloylamino)benzenethiolato] 2 , were synthesized and the crystal structures were determined. The crystal structure of Hg[2-(pivaloylamino)benzenethiolato] 2 ‚ 1 / 2 H 2 O shows the presence of two distinct conformers with different C-S-(Hg)-S-C torsion angles (81.7 and 176.6°). The crystal structure of Hg[2,6-bis(pivaloylamino)benzenethiolato] 2 indicates the presence of ordinary Hg-S bonds (2.335-( 2) and 2.342(2) Å) and a straight linear coordination (S-Hg-S ) 174.7(1)°) with a weak interaction of one of the amide CO groups toward Hg(II). A weak NH---S hydrogen bond in both complexes is detected from the IR spectra in the solid state. The 199 Hg NMR spectra show the high-field shift with a decrease in the S f Hg(II) ligand-to-metal charge transfer by the NH---S hydrogen bonding. The high-field shift by the double NH---S hydrogen bond is far greater than that by the p-substituent effect of the electron-withdrawing group (OMe, H, NHCOCH 3 , Cl, NO 2 ) on the benzenethiolate ring.

show abstract

“…~~ as well as for soluble complex species of the latter compound.' However the equilibrium constant, log K = -10.2, for reaction (10) compared to that (-8.03) reported" CCd(HA),I2 + e [Cd(HA),A] + + H + (10) for 2-aminoethane-1 -thiol clearly indicates that under these conditions the chelating ability of 3-aminopropane-1 -thiol is low. Probably, chelate formation is competing with deprotonation of complexed ligands.…”

Section: Discussionmentioning

confidence: 67%

Polymeric thiolate complexes in solution. Stability constants of the cadmium(II) complexes of 3-aminopropane-1-thiol

González-Duarte¹,

Vives²

1989

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

Complex formation between Cd" and 3-aminopropane-I -thiol has been studied b y means of nearly 425 e.m.f. measurements w i t h a glass electrode in 10 separate titrations at 25 "C in 3 mol dm-3 (sodium) perchlorate medium [+I O%(v/v) CH,OH]. Conclusions drawn from graphical methods based on the 'core + links' hypothesis and on the 'extended variation' technique are in accord with results obtained from the numerical treatment. Experimental data for 3 < -log [ H ' 3 < 11 can be explained b y assuming that the following complexes predominate over a wide p H range: [Cd( HA),I2+, [Cd,( HA),I6+, [Cd,( HA),],+, and [Cd,(HA),,]'O+, H A being the uncharged ligand. The deprotonation of these species gives rise to several mono-and poly-nuclear ternary complexes CdpAqHr, r < q, A denoting the deprotonated form of the ligand. Chelate formation seems very likely. Comparisons with other cadmium( 11)-mercaptoamine systems are made.The renewed interest in the chemistry of metal thiolate complexes is mainly due to the important role of the thiol group of the cysteinyl residues in metalloproteins' in co-ordinating metal atoms. Recent review^^.^ show that the amount of experimental data related to the structural features of those complexes has increased very much in the past years. While topological relationships have been proposed for several metal thiolate complexes4 and also new synthetic strategies have been developed,' it is still difficult to predict the stoicheiometry and the geometry of a complex with a given metal: thiol molar ratio.Solution equilibria studies of metal-thiol systems should help to make accurate predictions but they are practically impossible in aqueous solutions unless the problem of the low solubility of metal thiolates is overcome. The introduction of a non-co-ordinating solubilizing group in the thiol molecule led us in the past to choose y-mercaptoamines as models for the behaviour of simple thiol ligands. The stability constants of the complexes formed between 4-mercapto-1-methylpiperidine and Zn116 and Cd117 as well as the crystal and molecular structures of several solid complexes of Zn11,8 Cd'I,' and Hg" with different y-mercaptoamine ligands have been reported.In this paper we report the stability constants of the soluble complexes found potentiometrically while in the system cadmium(11)-3-aminopropane-1-thiol in water-methanol (9: 1 v/v). The results obtained are compared with those with 4-mercapto-1 -methylpiperidine' and with 2-aminoethane-1thiol.'

show abstract

Synthesis and vibrational spectra of[RSHgII]2+(ClO4)2 complexes. Crystal and molecular structure of bis(N-methylpiperidinium-4-thiolato)-mercury(II) perchlorate.

Cited by 36 publications

References 19 publications

Symmetrization of Phenylmercuric Hydroxides by the Action of Nickel(II) and Cobalt(II) Acetylacetonates. Isolation and Structural Characterization of an Intermediate in This Reaction

Symmetrization of Phenylmercuric Hydroxides by the Action of Nickel(II) and Cobalt(II) Acetylacetonates. Isolation and Structural Characterization of an Intermediate in This Reaction

Effect of the NH---S Hydrogen Bond on the Nature of Hg−S Bonding in Bis[2-(acylamino)benzenethiolato]mercury(II) and Bis[2,6-bis(acylamino)benzenethiolato]mercury(II) Complexes

Polymeric thiolate complexes in solution. Stability constants of the cadmium(II) complexes of 3-aminopropane-1-thiol

Contact Info

Product

Resources

About