Heterometallic Chains and Clusters with Gold-Transition Metal Bonds: Synthesis and Interconversion

Sculfort, Sabrina; Welter, Richard; Braunstein, Pierre

doi:10.1021/ic902245v

Cited by 24 publications

(27 citation statements)

References 156 publications

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“…This molecule is the first trimetallic cluster with such a n 2 -square geometry. 119 The Cu-Ag distances in 38 are in the range 2.734(1)-2.814(1) A ˚and are clearly shorter than the sum of the van der Waals radii for copper and silver (3.12 A ˚) or to the value of 2.9931 (12) A found in a dinuclear Ag-Au complex containing bridging ligands. 141 They are even comparable to the sum of the covalent radii of 2.77 A ˚for copper and silver.…”

Section: Intramolecular Heterometallic D 10 -D 10 Interactions In Het...mentioning

confidence: 93%

Intramolecular d10–d10 interactions in heterometallic clusters of the transition metals

2011

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Weak attractive interactions between closed shell metal ions have been increasingly studied in the last few years and are generally designated as metallophilic interactions. They are best evidenced in the solid state where structural data obtained by X-ray diffraction provide precise information about the distance between the metals involved. The strength of such metal-metal interactions has been compared to that of hydrogen bonding (ca. 7-11 kcal mol(-1)) and is clearly sufficient to bring about novel bonding and structural features and confer interesting physical properties such as luminescence, polychromism, magnetism or one-dimensional electrical conductivity. The Cu(I)-Cu(I), Ag(I)-Ag(I) and Au(I)-Au(I) interactions have been increasingly observed and the latter have certainly been the most studied. Early qualitative analyses of the aurophilic attraction focused on Au-Au bonding originating from 6s, 6p and 5d orbital mixing. Numerous theoretical studies on metallophilic interactions continue to be carried out at various levels of sophistication which take into account relativistic and correlation effects to describe these van der Waals-type interactions. In this critical review, we would like to focus on the synthesis and structures of heterometallic clusters of the transition metals in which intra- rather than intermolecular d(10)-d(10) interactions are at work, in order to limit the role of packing effects. We wish to provide the reader with a comparative overview of the metal core structures resulting from or favoring metallophilic interactions but do not intend to provide a comprehensive coverage of the literature. We will first examine heterometallic clusters displaying homometallic and then heterometallic d(10)-d(10) interactions. Although the focus of this review is on d(10)-d(10) interactions involving metals from the group 11, we shall also briefly examine for comparison some complexes displaying intramolecular d(10)-d(10) interactions involving metals from other groups (188 references).

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Section: Intramolecular Heterometallic D 10 -D 10 Interactions In Het...mentioning

confidence: 93%

Intramolecular d10–d10 interactions in heterometallic clusters of the transition metals

2011

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“…Precise control of these parameters can therefore give rise to a diversity of functions and associated applications in basic research and technology . Since the first reports of di‐ and trinuclear heterometallic clusters in the 1960s, larger nanoclusters have been developed with six nuclei (Mo 3 Cu 3 ), eight nuclei (Mo 4 M 4 , M=Ag, Au), 10 nuclear Zr 6 M 4 (M=Ni, Co) nanoclusters, and more than 100 nuclei in Au‐Ag nanoclusters . Heterometallic nanoclusters are often stabilized by periphery organic ligands .…”

Section: Methodsmentioning

confidence: 99%

Stabilizing and Organizing Bi₃Cu₄ and Bi₇Cu₁₂ Nanoclusters in Two‐Dimensional Metal–Organic Networks

et al. 2018

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Multinuclear heterometallic nanoclusters with controllable stoichiometry and structure are anticipated to possess promising catalytic, magnetic, and optical properties. Heterometallic nanoclusters with precise stoichiometry of Bi Cu and Bi Cu can be stabilized in the scaffold of two-dimensional metal-organic networks on a Cu(111) surface through on-surface metallosupramolecular self-assembly processes. The atomic structures of the nanoclusters were resolved using scanning tunneling microscopy and density functional theory calculations. The nanoclusters feature highly symmetric planar hexagonal shapes and core-shell charge modulation. The clusters are arranged as triangular lattices with a periodicity that can be tuned by choosing molecules of different size. This work shows that on-surface metallosupramolecular self-assembly creates unique possibilities for the design and synthesis of multinuclear heterometallic nanoclusters.

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“…in which these atoms are not bound to any ligand and are therefore only involved in homo- and/or heterometallic metal–metal bonding. A class of heterometallic complexes containing bare d 10 ions M from the group 11 metals is represented by trinuclear linear or bent chain complexes of the type M′–M–M′ where M′ is a transition or a post-transition metal . A further category contains complexes in which the group 11 d 10 ion bridges one or two metal–metal bonds, forming triangular or bow-tie clusters, respectively, caps one or two triangular metal faces, or serves as connector between metal polyhedra to form discrete or oligomeric species (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d¹⁰–d¹⁰ Interactions

et al. 2016

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A comparative study of the reactivity of the carbonylmetalates {m} − = [MoCp(CO) 3 ] − (Cp = η 5 -C 5 H 5 ) and [Mo(η 5 -C 5 H 4 NMe 2 )(CO) 3 ] − toward d 10 complexes of the group 11 metals, [Cu(NCMe) 4 ](BF 4 ), AgBF 4 and [N(n-Bu) 4 ][AuBr 2 ], has allowed the characterization of new heterometallic hexa-and octanuclear clusters with the same general formula [M{m}] n (M = Cu, Ag, Au). In these cyclic oligomers, the value of n depends of the coinage metal. Thus, the hexanuclear cluster [Cu 3 {Mo(η 5 -C 5 H 4 NMe 2 )(CO) 3 } 3 ] (17) has a planar metal core, formed by a copper triangle with edge-bridging molybdenum atoms. The octanuclear "star shape" clusters [Ag 4 {Mo(η 5 -C 5 H 4 NMe 2 )(CO) 3 } 4 ] ( 19) and [Au 4 {Mo(η 5 -C 5 H 4 NMe 2 )(CO) 3 } 4 ] (21) contain a square silver or gold core, respectively, edge-bridged by molybdenum atoms. In these three clusters, the 2-D raft-type structure of their metal core, which is ν 2 -triangular for Cu 3 Mo 3 and of a square-in-a-square-type for the octanuclear Ag 4 Mo 4 and Au 4 Mo 4 clusters, allows for d 10 −d 10 metallophilic interactions. The latter have been clearly evidenced by relatively short separations between the d 10 metal centers: average Cu•••Cu, Ag•••Ag, and Au•••Au distances of 2.617(1), 2.869(1) and 2.792(1) Å, respectively. These new carbonyl clusters are closely related to their Cp analogs previously reported and constitute a unique set of heterometallic clusters with such geometries involving group 6 and group 11 transition metals.

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Heterometallic Chains and Clusters with Gold-Transition Metal Bonds: Synthesis and Interconversion

Cited by 24 publications

References 156 publications

Intramolecular d10–d10 interactions in heterometallic clusters of the transition metals

Intramolecular d10–d10 interactions in heterometallic clusters of the transition metals

Stabilizing and Organizing Bi₃Cu₄ and Bi₇Cu₁₂ Nanoclusters in Two‐Dimensional Metal–Organic Networks

Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d¹⁰–d¹⁰ Interactions

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Heterometallic Chains and Clusters with Gold-Transition Metal Bonds: Synthesis and Interconversion

Cited by 24 publications

References 156 publications

Intramolecular d10–d10 interactions in heterometallic clusters of the transition metals

Intramolecular d10–d10 interactions in heterometallic clusters of the transition metals

Stabilizing and Organizing Bi3Cu4 and Bi7Cu12 Nanoclusters in Two‐Dimensional Metal–Organic Networks

Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d10–d10 Interactions

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Stabilizing and Organizing Bi₃Cu₄ and Bi₇Cu₁₂ Nanoclusters in Two‐Dimensional Metal–Organic Networks

Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d¹⁰–d¹⁰ Interactions