Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

Gualco, Pauline; Lin, Tzu‐Pin; Sircoglou, Marie; Mercy, Maxime; Ladeira, Sonia; Bouhadir, Ghenwa; Pérez, Lisa M.; Amgoune, Abderrahmane; Maron, Laurent; Gabbaı̈, François P.; Bourissou, Didier

doi:10.1002/anie.200905391

Cited by 116 publications

(34 citation statements)

References 53 publications

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“…The phosphorus center gives rise to a 31 P NMR resonance at À1.0 ppm (J SnÀP = 18.1 Hz) which can be compared to the value of À4 ppm observed for Ph 3 P. Interestingly, the 119 Sn NMR resonance appears as a singlet at À101.7 ppm, a chemical shift which is distinctly upfield from that observed for Ph 3 SnCl (À45 ppm) [9]. This situation is reminiscent of that encountered in the known ortho-(i-Pr 2 P)C 6 H 4 ) 2 SnPhCl (2) [10] which gives rise to a 119 Sn NMR resonance at À126.4 ppm. In fact, the 119 Sn NMR chemical shifts of 1 and 2 approach those reported for hypervalent tin species adducts such as [2-(Me 2 NCH 2 )C 6 H 4 ]SnPh 2 Cl (-176.9 ppm) [11] or ClPh 3 Sn-pyridine (À219 ppm) [12].…”

Section: Resultsmentioning

confidence: 57%

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Dative P→Sn interactions in ortho-phenylene phosphine-stannanes

Lin

Gualco

Ladeira³

et al. 2010

Comptes Rendus. Chimie

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Section: Resultsmentioning

confidence: 57%

“…ortho-(Ph 2 P)C 6 H 4 Li 1 [6d,8] and 2 [10] was prepared according to the reported procedures. Solvents were dried by passing through an alumina column (CH 2 Cl 2 ) or refluxing under N 2 over Na/K (Et 2 O and n-hexane).…”

Section: General Considerationsmentioning

confidence: 99%

Dative P→Sn interactions in ortho-phenylene phosphine-stannanes

Lin

Gualco

Ladeira³

et al. 2010

Comptes Rendus. Chimie

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“…[11] The most diagnostic features are the short Au À Si distance of 3.090(2) , a geometry around the silicon center that only deviates slightly from trigonal-bipyramidal, and the noticeable elongation of the Si À F bond (from 1.599(7) in free ligand 1 to 1.635(3) in complex 4). The pentacoordinate character of silicon in 4 was also apparent from NMR spectroscopic studies.…”

Section: Resultsmentioning

confidence: 99%

“…[11] Crystallographic data were collected on Bruker-Kappa APEX-II diffractometer (for 5 and 6) and Bruker-AXS APEX-II diffractometer (for 2 and 8) with Mo Ka radiation (l = 0.71073 ) at 180(2) K for 5, 100(2) K for 6, and 193(2) K for 2 and 8. In all cases, a suitable crystal was mounted on a glass fiber or nylon loop and shock-cooled on the goniometer head.…”

Section: Synthesis Of Complexmentioning

confidence: 99%

“…Starting from diphosphine-silanes and stannanes, we prepared gold complexes of general formula II. [11] Here, the Au!E (E= Si, Sn) interaction is supported by only two phosphorus buttresses, and the heavier Group 14 element adopts a trigonal-bipyramidal arrangement. These preliminary results prompted us to explore the influence of the substitution pattern at silicon on the coordination of silanes as s-acceptor ligands, and here we report a comprehensive study on a series of diphosphine-silane gold complexes [({o-(iPr 2 P)C 6 H 4 } 2 Si(R)X)AuCl] (R = F, Ph, Me, X = F, Me).…”

Section: Introductionmentioning

confidence: 99%

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Hypervalent Silicon Compounds by Coordination of Diphosphine–Silanes to Gold

Gualco

Mercy

Ladeira³

et al. 2010

Chemistry A European J

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Coordination of ambiphilic diphosphine-silane ligands [o-(iPr(2)P)C(6)H(4)](2)Si(R)F (R=F, Ph, Me) to AuCl affords pentacoordinate neutral silicon compounds in which the metal atom acts as a Lewis base. X-ray diffraction analyses, NMR spectroscopy, and DFT calculations substantiate the presence of Au→Si interactions in these complexes, which result in trigonal-bipyramidal geometries around silicon. The presence of a single electron-withdrawing fluorine atom is sufficient to observe coordination of the silane as a σ-acceptor ligand, provided it is positioned trans to gold. The nature of the second substituent at silicon (R=F, Ph, Me) has very little influence on the magnitude of the Au→Si interaction, in marked contrast to N→Si adducts. According to variable-temperature and 2D EXSY NMR experiments, the apical/equatorial positions around silicon exchange in the slow regime of the NMR timescale. The two forms, with the fluorine atom in trans or cis position to gold, were characterized spectroscopically and the activation barrier for their interconversion was estimated. The bonding and relative stability of the two isomeric structures were assessed by DFT calculations.

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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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Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

Cited by 116 publications

References 53 publications

Dative P→Sn interactions in ortho-phenylene phosphine-stannanes

Dative P→Sn interactions in ortho-phenylene phosphine-stannanes

Hypervalent Silicon Compounds by Coordination of Diphosphine–Silanes to Gold

The Chemistry of Gold–Metal Bonds

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