Amalgamating at the molecular level. A study of the strong closed-shell Au(i)⋯Hg(ii) interaction

López‐de‐Luzuriaga, José M.; Monge, Miguel; Olmos, M. Elena; Pascual, David; Lasanta, Tania

doi:10.1039/c1cc11036e

Cited by 50 publications

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“…5 Also, if we compare the Au I ···Hg II , Ag I ···Hg II , and Cu I ···Hg II heterometallic interactions with the corresponding Au I ···Hg II and Au III ···Hg II contacts studied previously in our research group in models 30 respectively, we observe similar interaction strengths regardless of the oxidation state of the gold center or the ligands bonded to this metal ion. The main difference of the latter with the models studied in this paper is the perhalophenyl group bonded to Au(I) instead of a phosphine ligand or the Au III fragment with two Cl and one C 6 F 5 groups.…”

Section: ■ Introductionsupporting

confidence: 56%

“…This type of interactions were first described by Schmidbaur in 1988, 4 and subsequently, theoretical studies quantified the strength of these interactions up to −57 kJ·mol −1 , a surprisingly strong value, from which a non-negligible 26% is due to relativistic effects. 5 These strong interactions made possible a high number of structural motifs, 2,6 and in addition, parallel to this, the complexes often displayed interesting optical properties. 7−9 In the case of other heavy atoms, although the contraction of the radius due to the relativistic effects is not so important as in gold, these effects also play an important role in their properties.…”

Section: ■ Introductionmentioning

confidence: 98%

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Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

et al. 2015

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Heteronuclear complexes PPh 2 ) 2 ]X (M = Au, X = ClO 4 (1); M = Ag, X = BF 4 (2); M = Ag, X = CF 3 CO 2 (3); M = Cu, X = Br (4)) were prepared by the treatment of [Hg(o-C 6 H 4 PPh 2 ) 2 ] with one equivalent of the corresponding coinage metal salt. Their crystal structures, determined by X-ray diffraction methods, display Hg II ··· M I (M = Au, Ag, Cu) contacts. Ab initio calculations show similar interaction energies (ca. 40 kJ·mol −1 ) and similar origin (dispersive forces) for these Hg···Au, Hg···Ag, and Hg···Cu interactions. ■ INTRODUCTIONNowadays, relativistic effects have shown an enormous importance to understand the chemical and physical properties of the heaviest 6s transition and post-transition metallic elements. From them, the element whose physical and chemical properties are more influenced by these effects is gold. 1−3 Probably, the most important structural consequence of the relativistic effects in gold is the high tendency to form closedshell interactions between gold(I) centers. This type of interactions were first described by Schmidbaur in 1988, 4 and subsequently, theoretical studies quantified the strength of these interactions up to −57 kJ·mol −1 , a surprisingly strong value, from which a non-negligible 26% is due to relativistic effects. 5 These strong interactions made possible a high number of structural motifs, 2,6 and in addition, parallel to this, the complexes often displayed interesting optical properties. 7−9 In the case of other heavy atoms, although the contraction of the radius due to the relativistic effects is not so important as in gold, these effects also play an important role in their properties. 10−14 Also, more recent studies on the relativity of the lead−acid or mercury batteries attribute a non-negligible 80% or 30%, respectively, of the electromotoric forces to the relativistic effects. 15,16 On the other hand, a logical next step in these studies was the study of the relativity in heteronuclear systems in which different metals maintain noncovalent interactions between them and in which at least one of them is a heavy 6s element, preferably gold. The synthesis of these complexes has been possible, making use of different synthetic strategies (acid− base, transmetalation, etc.). In such a way, a good number of heterometallic gold(I) compounds were described in which gold maintains an interaction with different closed shell ions such as Ag I , Bi III , Tl I , or Cu I , among others. 17−23 Thus, for instance, with the, in principle, more favorable coinage congeners, the energy of Au I ···Ag I and Au I ···Cu I contacts has been theoretically estimated to be 22 and 17 kJ·mol −1 , respectively. Besides, both of them have in common a high electronic correlation contribution probably induced by the relativistic effects present in gold. 24 In addition, the importance of the dispersive-type forces is evident in the intermetallic acid−base interactions that take place between gold(I) and thallium(I) or bismuth(III), which are, in both cases, around 20% of the total inter...

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Section: ■ Introductionsupporting

confidence: 56%

Section: ■ Introductionmentioning

confidence: 98%

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

et al. 2015

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“…In this way, the two conformers adopt Au‐Hg‐Au transoid and cisoid arrangements, respectively. Overall, the Au⋅⋅⋅Hg contacts of 6 (3.0253(4) to 3.4082(4) Å) are somewhat longer than the Au–Au contacts in 3 – 5 , but are close to intermolecular Au⋅⋅⋅Hg distances (3.097(2)–3.498(3) Å) observed recently for a number of so called molecular Au–Hg amalgams, as well as the intramolecular Au⋅⋅⋅Hg distances (3.112(1)–3.2940(9) Å) observed for some similar complexes . Complex 6 may be also regarded as a metallo‐pincer complex [ClHg( AuCAu )] between Hg II and the anionic tridentate ligand [2,6‐(Ph 2 PAuCl) 2 C 6 H 3 ] − ( AuCAu ) − containing a central carbanionic binding site and two “gold‐arms” contributing pincer‐type chelation through metallophilic interactions.…”

Section: Resultssupporting

confidence: 80%

Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d¹⁰–d¹⁰ Interactions

Olaru

Kögel

Aoki

et al. 2019

Chemistry A European J

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The reaction of 2,6‐F2C6H3SiMe3 with Ph2PLi provided 2,6‐(Ph2P)2C6H3SiMe3 (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6‐(Ph2P)2C6H3]− (PCP)−. The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6‐(Ph2PAuCl)2C6H3SiMe3 (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me3SiF and yielded the neutral tetranuclear complex linear‐[Au4Cl2(PCP)2] (3) comprising a string‐like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBArF4 (ArF=3,5‐(CF3)2C6H3) in the presence of tht, the formation of the dicationic tetranuclear complex linear‐[Au4(PCP)2(tht)2](BArF4)2 (4) was observed, in which the string‐like structural motif is retained. Irradiation of 4 with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex cyclo‐[Au4(PCP)2(tht)2](BArF4) (5), which comprises a rhomboidal motif of four Au atoms. In 3–5, the Au atoms are associated by a number of significant aurophilic interactions. The atom‐economic and selective reaction of 3 with HgCl2 yielded the neutral trinuclear bimetallic complex [HgAu2Cl3(PCP)] (6) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, 6 may be also regarded as a metallopincer complex [ClHg(AuCAu)] between HgII and the anionic tridentate ligand [2,6‐(Ph2PAuCl)2C6H3]− (AuCAu)− containing a central carbanionic binding site and two “gold‐arms” contributing pincer‐type chelation trough metallophilic interactions. Compounds 1–6 were characterized experimentally by multinuclear NMR spectroscopy and X‐ray crystallography and computationally using a set of real‐space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI‐D) as well as the Non‐Covalent Interaction (NCI) Index.

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“…All compounds were characterized by 1 H‐, 31 P‐, 19 F‐, and 13 C‐NMR spectroscopy, and were matched to literature reports where appropriate ( 1a , 1b , 1c , 2a , 2b , 2c , 3a are known, compounds 1d , 2d , 3b , 3c , 3d are novel). Our analysis of 3a differed slightly by 31 P‐NMR analysis where the literature gives a chemical shift of 3.28 ppm and we instead observed the resonance at –5.00 ppm after purifying the compound by vacuum sublimation.…”

Section: Resultsmentioning

confidence: 99%

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

et al. 2019

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Atomic layer deposition (ALD) of gold is being studied by multiple research groups, but to date no process using non‐energetic co‐reactants has been demonstrated. In order to access milder co‐reactants, precursors with higher thermal stability are required. We set out to uncover how structure and bonding affect the stability and volatility of a family of twelve organogold(I) compounds using a combination of techniques: X‐ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and density functional theory (DFT). Small, unsubstituted phosphonium ylide ligands bind more strongly to Au(I) than their silyl‐substituted analogues, but the utility of both these ligands suffers due to their poor volatility and substantial thermal decomposition. Pentafluorophenyl (C6F5) is introduced as a new, very electronegative ligand for gold vapor deposition precursors, and it was found that the disadvantage to volatility due to π‐stacking and other intermolecular interactions in the solid state was overshadowed by dramatic improvements to kinetic and thermodynamic stability. We introduce a new figure of merit to compare and rank the suitability of these and other complexes as precursors for vapor deposition. Finally, DFT calculations on four compounds that have high figures of merit show a linear correlation between the gold‐coordinative ligand bond dissociation energies and the observed decomposition temperatures, highlighting and justifying this design strategy.

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Amalgamating at the molecular level. A study of the strong closed-shell Au(i)⋯Hg(ii) interaction

Cited by 50 publications

References 23 publications

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d¹⁰–d¹⁰ Interactions

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

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Amalgamating at the molecular level. A study of the strong closed-shell Au(i)⋯Hg(ii) interaction

Cited by 50 publications

References 23 publications

Study of the Nature of Closed-Shell HgII···MI (M = Cu, Ag, Au) Interactions

Study of the Nature of Closed-Shell HgII···MI (M = Cu, Ag, Au) Interactions

Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d10–d10 Interactions

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

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Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d¹⁰–d¹⁰ Interactions