Chalcogenide clusters of Groups 8–10 noble metals

Sokolov, Maxim N.; Abramov, Pavel A.

doi:10.1016/j.ccr.2012.04.009

Cited by 37 publications

(8 citation statements)

References 105 publications

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“…M-M bonding is encountered in a wide variety of molecular compounds or crystalline systems such as bulk metals, alloys, superconducting materials, Zintl-Klemm phases. Although compounds featuring M-M bonds are known for many decades, the chemistry of M-M bonds is still a hot topic as attested by several reviews dedicated to recent advances in both main group and transition element chemistry [1][2][3][4][5]. Compounds with homometallic or heterometallic extended metal atom chains (EMACs) are considered as potential molecular wires [3,6,7].…”

Section: Introductionmentioning

confidence: 99%

Topological analysis of the metal-metal bond: A tutorial review

Lepetit

Fau

Fajerwerg

et al. 2017

Coordination Chemistry Reviews

121

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This contribution explains how the topological methods of analysis of the electron density and related functions such as the electron localization function (ELF) and the electron localizability indicator (ELI-D) enable the theoretical characterization of various metal-metal (M-M) bonds (multiple MM bonds, dative MM bonds). Examples are taken in both bulk metals, alloys and molecular complexes. Metallic bonds as well as weak partially covalent MM interactions, are described and characterized unambiguously combining AIM (atoms in molecules) and ELF/ELI-D topological analysis.

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Section: Introductionmentioning

confidence: 99%

Topological analysis of the metal-metal bond: A tutorial review

Lepetit

Fau

Fajerwerg

et al. 2017

Coordination Chemistry Reviews

121

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“…1 H NMR spectra were similar among the series and resonances of ortho ‐thiolate protons were between 6 and 7 ppm. This represents an upfield shift of 1 ppm compared to their usual resonances 9a,b. These shifts might be caused by the deshielding cone perpendicular to each metal‐aromatic core,5d although they can be also induced by π‐stacking interactions between aryl groups of thiolates and those of phosphines flanking them 12.…”

Section: Methodsmentioning

confidence: 95%

A Simple Synthesis of Triangular All‐Metal Aromatics Allowing Access to Isolobal All‐Metal Heteroaromatics

Wang

Deyris

Cañeque

et al. 2015

Chemistry A European J

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A simple synthetic method allows the one-pot assembly of C3 -symmetric, 44-core-valence-electron, triangular Pd or Pt clusters and their heterobimetallic mixed Pd/Pt analogues. These mixed metal complexes are the first examples of stable triangular all-metal heteroaromatics. In contrast to traditional heteroaromatic molecules formed combining main-group elements, they actually retain structural and electronic features of their homonuclear analogues.

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“…4 The development of rational synthetic methodologies has allowed the preparation of a wide range of metal-sulfur polynuclear compounds and clusters with the required metalsulfur framework. 5 In this context, hydrosulfido metal complexes are fundamental precursors for the controlled synthesis of sulfido-bridged homo-and heterometallic clusters. 6,7 In fact, we have reported the usefulness of the compounds [Cp 2 Ti(SH) 2 ] and [Cp tt 2 Zr(SH) 2 ] (Cp tt = η 5 -1,3-di-tert-butylcyclopentadienyl) as precursors for the synthesis of d 0 -d 8 sulfido-bridged ELHB complexes or clusters through additive deprotonation reactions with mono-and dinuclear d 8 rhodium and iridium compounds having protonable ligands.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of [TiM2] (M = Rh, Ir) and [TiIr3] early-late heterobimetallic sulfido-bridged clusters

Ciriano

Lahoz

Oro

et al. 2016

Journal of Organometallic Chemistry

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Please cite this article as: M.A. Casado, M.A. Ciriano, F.J. Lahoz, L.A. Oro, J.J. Pérez-Torrente, Reactivity of [TiM2] (M = Rh, Ir) and [TiIr3] early-late heterobimetallic sulfido-bridged clusters, Journal of Organometallic Chemistry (2015), Early-late sulfido-bridged clusters with [TiM 2 ] cores (M = Rh, Ir) form hydroxo-bridged earlylate compounds upon protonation with aqueous HCl. The sulfido-bridged cluster of [TiIr 3 ] core reacts with alkynes at the metallic triangle. Abstract Treatment of heterobimetallic sulfido-bridged complexes [Cp(acac)Ti(µ 3 -S) 2 {M(cod)} 2 ] (M = Rh (1), Ir (2)) with the organic acids CX 3 COOH (X = F, H) forms the corresponding acetate derivatives [Cp(CX 3 COO)Ti(µ 3 -S) 2 {M(cod)} 2 ] (X = F, M = Rh (3), Ir (4); X = H, M = Rh (5), M = Ir (6)). While complex 3 was easily isolated, compounds 4-6 establish in solution the corresponding equilibria with the starting complexes 1 and 2. Treatment of 1 with a hydrochloric acid solution in THF generates the heterohexanuclear cationic cluster [{CpTi(µ 3 -S) 2 Rh 2 (cod) 2 } 2 (µ-OH)][Cl] (7), which is deprotonated with weak bases affording the oxo derivative [{CpTi(µ 3 -S) 2 {Rh(cod)} 2 } 2 (µ 2 -O)] (8). Cluster 8, and the analogous with the ligand methylcyclopentadienyl [{(CpMe)Ti(µ 3 -S) 2 {Rh(cod)} 2 } 2 (µ 2 -O)] (9), can be synthesized from reaction of the respective complexes [Cp 2 Ti(SH) 2 ] and [(CpMe) 2 Ti(SH) 2 ] with the methoxo-bridged dinuclear complex [{Rh(µ-OMe)(cod)} 2 ] in the presence of water. A preliminary study of the molecular structure of 9 confirmed the formation of an almost linear array of the "Ti-O-Ti" subunit, in which each titanium atom supports two "Rh(cod)" moieties through two sulfido bridges. Further, the heterotetranuclear cluster M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 2 [CpTi(µ 3 -S) 3 Ir 3 (µ 2 -CO)(CO) 3 (PMe 3 ) 3 ] (10) reacts with alkynes at the triiridium metallic triangle. The reactions with activated alkynes, such as dimethyl acetylenedicarboxylate (or diethyl acetylenedicarboxylate) afford clusters [CpTi(µ 3 -S) 3 Ir 3 (µ 2 -η 1 -RO 2 CC=CCO 2 R){C(O)RO 2 CC=CCO 2 R}(CO) 3 (PMe 3 ) 3 ] (R = Me (11), Et (12)), which incorporate two molecules of alkyne. The X-ray molecular structure of 11 shows that one alkyne is cis-metallated to the metal-metal bonded iridium centres whereas the other is taking part of a iridacyclobutenone moiety resulting from the CO migratory insertion into a iridium-alkyne bond at the third iridium centre. However, reaction of 10 with phenylacetylene stops at the cluster [CpTi(µ 3 -S) 3 Ir 3 (µ 2 -η 1 -PhCCH)(CO) 3 (PMe 3 ) 3 ] (13), which contains only a cis-metallated olefin to two metal-metal bonded iridium atoms. The X-ray molecular structure of [CpTi(µ 3 -S) 3 Ir 3 (µ 2 -η 1 -PhCCH)(H)(CO) 3 (PMe 3 ) 3 ][BF 4 ] (14), the product resulting from protonation of 13 with HBF 4 ·OEt 2 shows that the [TiIr 3 ]core remains intact and that the olefin is indeed cis-metallated to the two metal-metal bonded iridium atoms, while the third iridium atom from the metall...

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Chalcogenide clusters of Groups 8–10 noble metals

Cited by 37 publications

References 105 publications

Topological analysis of the metal-metal bond: A tutorial review

Topological analysis of the metal-metal bond: A tutorial review

A Simple Synthesis of Triangular All‐Metal Aromatics Allowing Access to Isolobal All‐Metal Heteroaromatics

Reactivity of [TiM2] (M = Rh, Ir) and [TiIr3] early-late heterobimetallic sulfido-bridged clusters

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