Unprecedented η3-M3 coordination mode in a terpyridine ligand

Aguado, Javier E.; Gimeno, M. Concepción; Laguna, Antonio

doi:10.1039/b502515j

Cited by 27 publications

(26 citation statements)

References 29 publications

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“…A chiral luminescent Au 16 ring has been reported by reaction of [Au 2 Cl 2 (m-dppm)] with K 2 (pippzdc) (pippzdc ¼ piperazine-1,4-dicarbodithiolate) which gives the tetramer [Au 4 (pippzdc)(dppm) 2 ] 4 [160]. Gold(I) complexes with polydentate nitrogen ligands are also known, such as with the ferrocenyl-terpyridine ligand (Figure 1.26a) in which the ligand acts as tridentate [176], or the tetranuclear derivative with 2,2 0 -bibenzimidazolate (Figure 1.26b) [177], or the complexes obtained in the reaction of trans-1,2-bis (4-pyridyl)ethylene with [Au 2 (O 2 CCF 3 ) 2 {m-(PPh 2 ) 2 (CH 2 ) n }] which gives with n ¼ 2 the cyclic compound and with n ¼ 3 or 4 one-dimensional linear or U-shaped polymers (Figure 1.26c) [178]. The meta and para isomers present different stoichiometries and structures such as [Au 3 (1,3-S 2 C 6 H 4 )(PPh 3 ) 3 ] þ , which shows a one-dimensional aggregate through head-to-tail aurophilic interactions or the Other types of polydentate ligands are those with different donor atoms that can be of the type P,C or N,C or S,S,C,C or P,N, and so on, [172][173][174][175].…”

Section: Gold(i) Complexes With Polydentate Ligandsmentioning

confidence: 95%

The Chemistry of Gold

Gimeno

2008

Modern Supramolecular Gold Chemistry

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Section: Gold(i) Complexes With Polydentate Ligandsmentioning

confidence: 95%

The Chemistry of Gold

Gimeno

2008

Modern Supramolecular Gold Chemistry

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“…[Au(C 6 F 5 )(FcCH 2 PPh 2 )] [154], [Au(C 6 F 5 ){Fc(EPh)PPh 2 }] (E = S, Se) [155] and [{Au(C 6 F 5 )} 3 ( 3 -Fcterpy)] [161] do not display Au· · ·Au interactions either (the shortest gold-gold distance in the former is 5.560Å), but there are intramolecular Au· · ·Au interactions of 3.0678(6) and 3.1559(7)Å in the terpy derivative that may contribute to the overall stability of the system (Fig. 19a), as was shown by DTF calculations [161], and intermolecular aurophilic contacts (see Table 1) that led to association into pairs in [Au(C 6 F 5 )(Fcpy)] [151] (Fig. 19b) and [Au(C 6 F 5 )(FcCH 2 pz)] [152] or into chains in the case of [Au(C 6 F 5 )(FcCH 2 NHpyMe)] [153] (Fig.…”

Section: Ferrocene Derivatives As Ligandsmentioning

confidence: 99%

“…(24) The crystal structures of half the Au I /Fe II complexes have been determined by X-ray diffraction methods, showing a typical linear environment for the gold(I) center, nearly eclipsed aromatic rings at iron, and none of them display intramolecular Au· · ·Fe interactions. [Au(C 6 F 5 )(FcCH 2 PPh 2 )] [154], [Au(C 6 F 5 ){Fc(EPh)PPh 2 }] (E = S, Se) [155] and [{Au(C 6 F 5 )} 3 ( 3 -Fcterpy)] [161] do not display Au· · ·Au interactions either (the shortest gold-gold distance in the former is 5.560Å), but there are intramolecular Au· · ·Au interactions of 3.0678(6) and 3.1559(7)Å in the terpy derivative that may contribute to the overall stability of the system (Fig. 19a), as was shown by DTF calculations [161], and intermolecular aurophilic contacts (see Table 1) that led to association into pairs in [Au(C 6 F 5 )(Fcpy)] [151] (Fig.…”

Section: Ferrocene Derivatives As Ligandsmentioning

confidence: 99%

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Perfluoroarylgold complexes

Fernández

Laguna

Olmos

2008

Coordination Chemistry Reviews

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“…Some CÀHÁ Á ÁAu contacts have also been described in gold complexes with ferrocenyl derivatives as ligands, such as those included in Table 5.2 containing 1-(diphenylphosphino)-1 0 -(phenylsulfanyl)ferrocene, 1-(diphenylphosphino)-1 0 -(phenylselenyl)ferrocene [41], (ferrocenylmethyl)phosphine [59], (ferrocenylmethyl) pyrazole [60] or 4 0 -ferrocenyl-2,2 0 :6 0 ,2 00 -terpyridine [61]. Figure 5.30 displays the secondary contacts (CÀHÁ Á ÁAu and CÀHÁ Á ÁCl) in [AuCl(PPh 2 CH 2 Fc)] [59], which give rise to layers in the solid state.…”

Section: Hydrogen Bonds: Auá á áHànm Interactionsmentioning

confidence: 99%

Supramolecular Architecture by Secondary Bonds

Olmos

2008

Modern Supramolecular Gold Chemistry

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Since the metal center in gold complexes usually displays acid character, AuÁ Á ÁNM contacts will be more easily formed as the basicity of the non-metal increases. Thus, there are many goldÁ Á Áhalogen weak interactions between cationic gold complexes and halides or anions of which the halogen forms part, but most are individual contacts between ions that do not generate supramolecular structures. For example, about 50% of AuÁ Á ÁCl contacts are isolated cationÁ Á Áanion interactions.Nevertheless, in some cases, cationÁ Á Áanion contacts give rise to extended structures, as in both the colorless and the yellow polymorph of [Au(C:NC 6 H 11 ) 2 ][PF 6 ] [13], where the gold cations aggregate via aurophilic contacts into infinite linear chains, which are further connected through AuÁ Á ÁF contacts to afford two-dimensional 296j 5 Supramolecular Architecture by Secondary Bonds adjacent molecules, 3.695(1) Å, is slightly longer than the sum of the van der Waals radii.Apart from these types of associations observed in certain neutral gold(I) products, one-dimensional polymers can be formed by AuÁ Á ÁCl interactions between ions, which are more often found when the gold(III) anion [AuCl 4 ] À is present, as occurs, for example, in [EMIM][AuCl 4 ] and [BMIM][AuCl 4 ] ([EMIM]þ ¼ 1-ethyl-3methylimidazolium, [BMIM]þ ¼ 1-(n-butyl)-3-methylimidazolium) [17]. Both salts are very similar in the solid state with each ion surrounded by eight counterions in a cubic fashion and containing two crystallographically independent [AuCl 4 ] À anions arranged perpendicularly to one another and connected by AuÁ Á ÁCl contacts. This results in infinite anionic chains of alternating corner-to-face arranged [AuCl 4 ] À units (Figure 5.5), a unique pattern in salts containing purely tetrachloroaurate(III) anions. The interionic AuÁ Á ÁCl distances in the EMIM and BMIM derivatives are 3.356(3) and 3.452(3) Å, respectively, the latter very close to the sum of the van der Waals radii of gold and chlorine (3.41 Å). In the mixed-valent compound [Au(terpy)Cl] 2 [AuCl 2 ] 3 [AuCl 4 ] [18], an infinite chain of gold containing anions and cations is generated through two types of weak interactions: aurophilic contacts, which result in pentanuclear units, and AuÁ Á ÁCl interactions ( Figure 5.6). Three [AuC1 2 ] À anions, arranged in a spiral, bridge two [Au(terpy)C1] 2þ cations through long axial contacts. The remaining axial site of the [Au(terpy)Cl] 2þ cation is occupied by a chlorine atom from a square-planar [AuC1 4 ] À anion at distance of 3.401(4) Å, resulting in a polymeric Á Á ÁCl-Au III -ClÁ Á ÁAu III Á Á ÁAu I Á Á ÁAu I Á Á ÁAu I Á Á ÁAu III Á Á ÁCl-Au III -ClÁ Á Á chain.A more complicated extended structure is present in [Au(HDMG) 2 ][AuCl 4 ] (H 2 DMG¼dimethylglyoxime, HON¼C(Me)C(Me)¼NOH) [19], where onedimensional polymers are formed via interionic AuÁ Á ÁCl contacts of 3.323(4) and Figure 5.5

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Unprecedented η3-M3 coordination mode in a terpyridine ligand

Cited by 27 publications

References 29 publications

The Chemistry of Gold

The Chemistry of Gold

Perfluoroarylgold complexes

Supramolecular Architecture by Secondary Bonds

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