Crystal and molecular structures of tri(o-tolyl)phosphinegold(I) purine-6-thiolate ethanol solvate (1/1) and tri(c-hexyl)phosphinegold(I) 6-methyl-2-thiouracilate

Cookson, Peter D.; Tiekink, Edward R. T.

doi:10.1007/bf01668245

Cited by 11 publications

(3 citation statements)

References 16 publications

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“…Generally, the Table 3 Crystallographic data and refinement details for R 3 PAu[SC(OMe)¼NR 0 ] for R ¼ Ph, o-tol, m-tol or p-tol, and R In terms of crystal packing, the above demonstrates that it is possible to fine-tune the ligand donor properties to allow the formation of aurophilic interactions, as in the structure of p-tol 3 PAu[SC(OMe)¼NC 6 H 4 NO 2 -4] (10). The influence of the thiolate ligand in dictating the formation of aurophilic interactions needs to be stressed here as in none of the previously reported o-tol 3 PAuX, 39,79,[158][159][160][161][162][163][164][165] m-tol 3 PAuX, [166][167][168] and p-tol 3 PAuX 63,124,164,169-174 structures have aurophilic interactions been found, i.e. regardless of the phosphine ligand or nature of X.…”

Section: Discussionmentioning

confidence: 93%

Electronic and steric control over Au⋯Au, C–H⋯O and C–H⋯π interactions in the crystal structures of mononuclear triarylphosphinegold(i) carbonimidothioates: R3PAu[SC(OMe)=NR′] for R = Ph, o-tol, m-tol or p-tol, and R′ = Ph, o-tol, m-tol, p-tol or C6H4NO2-4

Kuan

Tadbuppa

et al. 2008

CrystEngComm

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Section: Discussionmentioning

confidence: 93%

Electronic and steric control over Au⋯Au, C–H⋯O and C–H⋯π interactions in the crystal structures of mononuclear triarylphosphinegold(i) carbonimidothioates: R3PAu[SC(OMe)=NR′] for R = Ph, o-tol, m-tol or p-tol, and R′ = Ph, o-tol, m-tol, p-tol or C6H4NO2-4

Kuan

Tadbuppa

et al. 2008

CrystEngComm

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“…The square-planar co-ordination sphere of gold is slightly distorted with a maximum deviation of 0.08 Å for the donor atoms. The gold atom is situated only 0.022(3) Å out of the mean plane formed by C(1),Cl(1),N(27) and S (20). The phenyl ring of the Hdamp-C 1 ligand is twisted against the co-ordination sphere by 84.07Њ.…”

Section: Resultsmentioning

confidence: 99%

Reactions of dichloro[2-(dimethylaminomethyl)phenyl-C1,N ]gold(III), [Au(damp-C1,N )Cl2], with heterocyclic thiols. Evidence for Au–N bond cleavage and protonation of the dimethylamino group

Abram¹,

Mack²,

Ortner³

et al. 1998

J. Chem. Soc., Dalton Trans.

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Dichloro[2-(dimethylaminomethyl)phenyl-C 1 ,N]gold(), [Au(damp-C 1 ,N)Cl 2 ], reacts with 2-mercapto-1,3thiazoline (HSthiaz), 2-mercaptopyridine (HSpy), sodium 1-methylmercaptotetrazolate (NaSmetetraz), 4-methyl-3-mercapto-1,2,4-triazole (HSmetriaz) or 6-mercaptopurine (HSpur) under cleavage of the Au᎐N bond and protonation of the dimethylamino group. Compounds of general formulae [Au(Hdamp-C 1 )Cl(HL) 2 ] 2ϩ (HL = HSthiaz or HSpy), [Au(Hdamp-C 1 )Cl(L)] (L = Spur Ϫ ) or [Au(Hdamp-C 1 )(L) 3 ] (L = Smetetraz Ϫ ) have been isolated and characterized. The reaction with HSmetriaz leads to a rapid reduction of the metal and the formation of the gold() complex [Au(HSmetriaz) 2 ] ϩ . The crystal structures of [Au(Hdamp-C 1 )Cl(HSthiaz) 2 ]Cl 2 ؒMe 2 CO, [Au(Hdamp-C 1 )Cl(HSpy) 2 ]ؒH 2 O, [Au(Hdamp-C 1 )(Smetetraz) 3 ] and [Au(Hdamp-C 1 )Cl(Spur)]Cl have been elucidated showing the gold atoms in distorted square-planar co-ordination environments. Generally, one or more hydrogen atoms of the heterocyclic ligands and/or the NMe 2 H ϩ group form hydrogen bonds in the solid-state structures. The reaction of Na[AuCl 4 ] with Na(Smetetraz) and [NEt 4 ]Br yields bright red crystals of [NEt 4 ][Au(Smetetraz) 4 ], the first structurally characterized gold() complex with four monodentate thiolate ligands. The structure of the complex shows well separated [Au(Smetetraz) 4 ] Ϫ anions with Au᎐S distances of 2.354(4) Å. Square-planar gold() complexes containing 2-(dimethylaminomethyl)phenyl-C 1 ,N, (damp-C 1 ,N) Ϫ , have been known since 1984. 1 Key compounds are the dichloro and diacetato complexes [Au(damp-C 1 ,N)Cl 2 ] (1a) and [Au(damp-C 1 ,N )-(CH 3 CO 2 ) 2 ] 1 (1b) which recently have been studied by structural analysis 2 showing distorted square-planar co-ordination spheres for the gold atoms. During ligand exchange reactions the chloro or acetato ligands are preferably replaced. 2-9 Only a few examples are reported where the Au᎐N bond is cleaved. 9 However, to our knowledge, protonation of the liberated N(CH 3 ) 2 group has not yet been observed for gold compounds.

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“…[20] A large number of mixed ligand species of the type R 3 P-Au(I)-S=R' have also attracted interest, due to their potential for biological and photophysical applications. [21,22,23,24,25] Thiosemicarbazones and their metal complexes have been the subject of numerous studies because of their chemical and biological properties. The square planar gold(III) complexes with thiosemicarbazones and complexes containing both gold(III) and gold(I) centers are known.…”

Section: A N U S C R I P Tmentioning

confidence: 99%

Persistence of oxidation state III of gold in thione coordination

Jääskeläinen

Koskinen

Kultamaa

et al. 2017

Solid State Sciences

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Ligands N,N´-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl 3 (N,N´-tetramethylthiourea)] (1) and [AuCl 3 (2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak intra-and intermolecular interactions present in the solid state structures. The nature of the interactions was further investigated by topological charge density analysis via the QTAIM method. • Thione derivatives of gold were synthesized and characterized • Oxidation state III was atypically maintained • Computational TD-DFT studies were used to explain spectroscopic data • DFT and QTAIM methods were employed to clarify the oxidation state of the metal and the weak interactions in solid state

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Crystal and molecular structures of tri(o-tolyl)phosphinegold(I) purine-6-thiolate ethanol solvate (1/1) and tri(c-hexyl)phosphinegold(I) 6-methyl-2-thiouracilate

Cited by 11 publications

References 16 publications

Electronic and steric control over Au⋯Au, C–H⋯O and C–H⋯π interactions in the crystal structures of mononuclear triarylphosphinegold(i) carbonimidothioates: R3PAu[SC(OMe)=NR′] for R = Ph, o-tol, m-tol or p-tol, and R′ = Ph, o-tol, m-tol, p-tol or C6H4NO2-4

Electronic and steric control over Au⋯Au, C–H⋯O and C–H⋯π interactions in the crystal structures of mononuclear triarylphosphinegold(i) carbonimidothioates: R3PAu[SC(OMe)=NR′] for R = Ph, o-tol, m-tol or p-tol, and R′ = Ph, o-tol, m-tol, p-tol or C6H4NO2-4

Reactions of dichloro[2-(dimethylaminomethyl)phenyl-C1,N ]gold(III), [Au(damp-C1,N )Cl2], with heterocyclic thiols. Evidence for Au–N bond cleavage and protonation of the dimethylamino group

Persistence of oxidation state III of gold in thione coordination

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