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A hexanuclear gold carbonyl cluster.

ABSTRACT: The hexanuclear gold carbonyl cluster [PPh₄]₂[Au₆(CF₃)₆Br₂(CO)₂] (4) has been obtained by spontaneous self-assembly of the following independent units: CF₃AuCO (1) and [PPh₄][Br(AuCF₃)₂] (3). The cyclo-Au₆ aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ?310 pm), exhibits a cyclohexane-like arrangement with chair conformation. These aurophilic interactions also result in significant ?(CO) lowering: from 2194 cm^-1 in the separate component 1 to 2171 cm^-1 in the mixed aggregate 4. Procedures to prepare the single-bridged dinuclear component 3 as well as the mononuclear derivative [PPh₄][CF₃AuBr] (2) are also reported.

SUBMITTER: Martinez-Salvador S

PROVIDER: S-EPMC5505037 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature

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A hexanuclear gold carbonyl cluster.

Martínez-Salvador Sonia S Falvello Larry R LR Martín Antonio A Menjón Babil B

Chemical science 20150615 10

The hexanuclear gold carbonyl cluster [PPh4]2[Au6(CF3)6Br2(CO)2] (4) has been obtained by spontaneous self-assembly of the following independent units: CF3AuCO (1) and [PPh4][Br(AuCF3)2] (3). The cyclo-Au6 aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ∼310 pm), ...[more]

PMID: 28717445

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Project description:A new hexanuclear iron-selenium nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)Se(6)(NO)(6)] (1), and a hexanuclear iron-sulfur nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)S(6)(NO)(6)] (2), were synthesized by the solvent-thermal reactions of [(n-Bu)(4)N][Fe(CO)(3)NO] with selenium or sulfur in methanol, while a tetranuclear iron-sulfur nitrosyl cluster, (Me(4)N)[Fe(4)S(3)(NO)(7)] (3), was also prepared by the solvent-thermal reaction of FeCl(2).4H(2)O with thiourea in the presence of (CH(3))(4)NCl, NaNO(2), and methanol. Complexes 1-3 were characterized by IR, UV-vis, (1)H NMR, electrochemistry, and single-crystal X-ray diffraction analysis. IR spectra of complexes 1 and 2 show the characteristic NO stretching frequencies at 1694 and 1698 cm(-1), respectively, while the absorptions of complex 3 appear at 1799, 1744, and 1710 cm(-1). The UV-vis spectra of complexes 1-3 show different bands in the range of 259-562 nm, which are assigned to the transitions between orbitals delocalized over the Fe-S cluster, the ligand-to-metal charge transfer, pi*(NO)-d(Fe), and the metal-to-ligand charge transfer, d(Fe)-pi*(NO). Single-crystal X-ray structural analysis reveals that complex 1 crystallizes in the monoclinic P2(1)/n space group with two molecules per unit cell. Two parallel "chair-shaped" structures, consisting of three iron and three selenium atoms, are connected by Fe-Se bonds with an average distance of 2.341 A; each iron center is bonded to three selenium atoms and a nitrogen atom from the nitrosyl ligand with a pseudotetrahedral center geometry. Cyclic voltammograms of complexes 1 and 2 display two cathodic and three anodic current peaks with an unusually strong cathodic peak. Further electrochemical investigations demonstrated that the intensity of the unusually strong peak is a result of at least three processes. One is the quasi-reversible reduction, and the other two are from an irreversible electrochemical process, in which the compound goes through a typical electron transfer and chemical reaction mechanism. Compound 3 shows three quasi-reversible reductions.

Dataset Information

A hexanuclear gold carbonyl cluster.

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A hexanuclear gold carbonyl cluster.

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