Synthesis of homo- and heteronuclear ruthenium–gold clusters with diphosphine and thiolato bridged ligands. Single crystal molecular structure of [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] and [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)]

Hernández-Cruz, María G.; Sánchez-Cabrera, Gloria; Hernández–Sandoval, Micaela; Leyva, Marco A.; Rosales-Hoz, Marı́a J.; Ordoñez–Flores, Berenice A.; Salazar, Verónica; Lara, Alfredo Guevara; Zuno–Cruz, Francisco J.

doi:10.1016/j.jorganchem.2010.11.034

Cited by 6 publications

(1 citation statement)

References 34 publications

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“…In polyhydridic dinuclear species such as Re 2 H 8 (PPh 3 ) 4 and Re 3 H 5 (CO) 9 PPh 3 , partial H + /[LAu] + exchange was cleanly achieved to give, for example, Re 2 H 6 (PPh 3 ) 4 (AuPPh 3 ) 2 and Re 3 H 4 (CO) 9 (PPh 3 )(AuPPh 3 ), respectively, while both substitution and addition were observed with the mononuclear complex ReH 7 (PPh 3 ) 2 . In all three cases the isolobal units were accommodated in analogous structural positions (terminal or bridging), − and this was also observed in the conversion of (μ 3 -BrC)Ru 3 H 3 (CO) 9 into (μ 3 -BrC)Ru 3 H(CO) 9 (AuPPh 3 ) 2 and for the isostructural pairs Os 3 (CO) 10 (μ-Cl)(μ-H) and Os 3 (CO) 10 (μ-Cl)(μ-AuPPh 3 ) and some ruthenium analogues …”

Section: Isolobality Relations In Gold Compounds Of the Transition Me...mentioning

confidence: 67%

Gold Chemistry Guided by the Isolobality Concept^†

2011

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The general isolobality concept presented by Hoffmann, Stone, and Mingos in the early 1980s has hadtacitly or explicitlya great impact on the development of many areas of inorganic, organometallic, and coordination chemistry. Pertinent considerations were fruitful especially in gold chemistry, because isolobal relations between gold(I) cations [Au]+ and their complexes [LAu]+ on the one hand and protons [H]+, various carbocations [R]+, and other simple species on the other are particularly obvious. Work guided by these relationships has included almost all fields of gold chemistry, from simple high-energy species in the gas phase to homoatomic clusters of gold atoms or heteroatomic aggregates with main-group and transition elements. Recent work has also concentrated on the specific mechanisms of reactions catalyzed either by protons or by the above gold cations with a variety of new ligands L in separate or tandem reaction sequences. The present review summarizes classical and current lines of research that have followed the original concept up to its present frontier version of “autogenic isolobality”.

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Section: Isolobality Relations In Gold Compounds Of the Transition Me...mentioning

confidence: 67%

Gold Chemistry Guided by the Isolobality Concept^†

2011

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The Chemistry of Gold–Metal Bonds

Silvestru

Laguna

2015

Patai's Chemistry of Functional Groups

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This chapter summarizes the preparation, structural characterization and properties of heterometallic gold compounds built through metal–metal interactions or bonds. They are mainly synthesized following four different strategies. Two of them use the acid‐base process with gold precursors acting as acids or organoaurates acting as bases, the third one consists of the use of bidentate bridging ligands, and the fourth uses the isolobal relationship between the [(R 3 P)Au] + cations and the proton in carbonyl clusters. The structural behavior of these complexes has been studied by different methods, mainly Mössbauer spectroscopy, nuclear magnetic resonance spectroscopy, and single‐crystal X‐ray diffraction. Their structures show discrete molecules, extended linear chains or even two‐ or three‐dimensional networks. Many of these complexes display luminescence and the emissions are strongly dependent on their structures. Some theoretical calculations are able to show that the formation of metal–metal interactions or bonds, as well as the gold environments, are the main aspects that affect the energy of the emissions. Other very promising areas of research such as the potential applications in electrochemistry, in biology (antiproliferative and antitumoral activity) or as homogeneous and heterogeneous catalysts are also discussed.

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A Systematic Density Functional Theory Study of the Complete De-ligation of Ru₃(CO)₁₂

White

Bennett

Golovko³

et al. 2016

ChemistrySelect

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Ru3(CO)12 was systematically de‐ligated computationally and the energetic minima for all structures were calculated using density functional theory at the M06/SDD/cc‐pvdz level of theory. The lowest energy electronic configuration of the clusters Ru3(CO)12 to Ru3(CO)3 was found to be a singlet state, while for Ru3(CO)2, Ru3(CO)1 and Ru3 the minimum spin state was predicted to be quintet, septet, and nonet, respectively. The CO binding energies for all structures was found to increase approximately linearly with de‐ligation from Ru3(CO)12 to Ru3(CO)5, whereupon the binding energy decreased from this structure to Ru3CO. The average bond length of terminally bound CO ligands on each cluster was found to be larger than free carbon monoxide in all cases, and increased from 1.147 Å for Ru3(CO)12, to 1.161 Å for Ru3CO.

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Synthesis of homo- and heteronuclear ruthenium–gold clusters with diphosphine and thiolato bridged ligands. Single crystal molecular structure of [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] and [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)]

Cited by 6 publications

References 34 publications

Gold Chemistry Guided by the Isolobality Concept^†

Gold Chemistry Guided by the Isolobality Concept^†

The Chemistry of Gold–Metal Bonds

A Systematic Density Functional Theory Study of the Complete De-ligation of Ru₃(CO)₁₂

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Synthesis of homo- and heteronuclear ruthenium–gold clusters with diphosphine and thiolato bridged ligands. Single crystal molecular structure of [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] and [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)]

Cited by 6 publications

References 34 publications

Gold Chemistry Guided by the Isolobality Concept†

Gold Chemistry Guided by the Isolobality Concept†

The Chemistry of Gold–Metal Bonds

A Systematic Density Functional Theory Study of the Complete De-ligation of Ru3(CO)12

Contact Info

Product

Resources

About

Gold Chemistry Guided by the Isolobality Concept^†

Gold Chemistry Guided by the Isolobality Concept^†

A Systematic Density Functional Theory Study of the Complete De-ligation of Ru₃(CO)₁₂