Cleavage of ferrocenylbutadiynyl on a rhenium-gold cluster: Synthesis and molecular structure of Re4(AuPPh3)(μ4-C2)(μ3-C2Fc)(NCMe)(CO)13

Chedia, Roin; Dolgushin, Fedor M.; Smol’yakov, Alexander F.; Lekashvili, Oliko; Kakulia, Tsiala V.; Janiashvili, L. K.; Шелоумов, А. М.; Ezernitskaya, M. G.; Peregudova, Svetlana M.; Petrovskii, P. V.; Koridze, A. A.

doi:10.1016/j.ica.2011.08.045

Cited by 5 publications

(2 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The molecule contains two Re(CO) 4 groups linked by two bridging AuPPh 3 groups. The two independent Re–Au bond distances, Re1–Au1 = 2.7914(2) Å and Re1–Au1* = 2.7977(2) Å, are similar to those found in the compounds Re 2 (CO) 8 [μ-Au(PPh 3 )](μ-C 2 Ph), 2.744(1) and 2.844(2) Å, and Re 2 (CO) 8 [μ-Au(PPh 3 )](μ-C 4 Fc) (Fc = ferrocenyl), 2.7369(3) and 2.8268(3) Å. The Re–Re distance in 1 is 2.9070(3) Å, which is significantly shorter than the Re–Re single bond distance found in Re 2 (CO) 10 : Re–Re = 3.041(1) Å .…”

Section: Results and Discussionsupporting

confidence: 72%

“…24 Time-dependent DFT (TDDFT) calculations were performed for models in the gas phase by using the PBEsol functional with the same basis sets. 26 (Fc = ferrocenyl), 2.7369(3) and 2.8268(3) Å. The Re−Re distance in 1 is 2.9070(3) Å, which is significantly shorter than the Re−Re single bond distance found in Re 2 (CO) 10 : Re−Re = 3.041(1) Å.…”

Section: ■ Experimental Sectionmentioning

confidence: 81%

See 1 more Smart Citation

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

2013

View full text Add to dashboard Cite

The compounds Re2(CO)8(μ-AuPPh3)2, 1, a dimer of Re(CO)4(μ-AuPPh3), and ax,ax-Re2(CO)8(PPh3)2 were obtained from UV–vis radiation-induced decarbonylation of the compound Re(CO)5[Au(PPh3)]. Compound 1 contains two rhenium atoms bridged by two AuPPh3 groups. The complex has 32 valence electrons and is formally unsaturated by the amount of two electrons. The Re–Re bond distance in 1 is unusually short (Re–Re = 2.9070(3) Å), as found by a single-crystal structural analysis. The nature of the metal–metal bonding in 1 was investigated by DFT computational analyses, which have provided evidence not only for σ-bonding but also significant complementary π-bonding directly between the two rhenium atoms. The electronic structure of Re2(CO)8(μ-H)2, 2, was similarly analyzed and is compared with that of 1. Compound 1 is intensely colored due to low-energy, metal-based electronic transitions between the HOMO and HOMO-2 and the LUMO. Compound 1 reacts with I2 to yield Re2(CO)8(μ-AuPPh3)(μ-I), 3, and the known compound Re2(CO)8(μ-I)2, 4, by substitution of the bridging AuPPh3 groups with bridging iodide ligands. Compound 3 is electronically saturated, 34 valence electrons, and contains a formal Re–Re single bond: Re–Re = 3.2067(5) Å. Compound 3 was also in a high yield (83%) from the reaction of Re2(CO)8(μ-H)(μ-CHCHC4H9) with Au(PPh3)I. The Re–Re bonding in compounds 3, 4, and Re2(CO)10 was also analyzed computationally, and this bonding was compared with their bonding in 1 and 2.

show abstract

Section: Results and Discussionsupporting

confidence: 72%

Section: ■ Experimental Sectionmentioning

confidence: 81%

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

2013

View full text Add to dashboard Cite

show abstract

The Chemistry of Gold–Metal Bonds

Silvestru

Laguna

2015

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

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.

show abstract

Carbonyl and Isocyanide Complexes of Rhenium

Cheng

2022

Comprehensive Organometallic Chemistry IV

View full text Add to dashboard Cite

Cleavage of ferrocenylbutadiynyl on a rhenium-gold cluster: Synthesis and molecular structure of Re4(AuPPh3)(μ4-C2)(μ3-C2Fc)(NCMe)(CO)13

Cited by 5 publications

References 17 publications

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

The Chemistry of Gold–Metal Bonds

Carbonyl and Isocyanide Complexes of Rhenium

Contact Info

Product

Resources

About