Carbon−Carbon Coupling via Nucleophilic Addition of a Gold(I) Methanide Complex to Heterocumulenes

Bardajı́, Manuel; Gimeno, M. Concepción; Jones, Peter G.; Laguna, Antonio; Laguna, Mariano; Merchán, and Francisco; Romeo, Inocencio

doi:10.1021/om960893x

Cited by 15 publications

(5 citation statements)

References 24 publications

(21 reference statements)

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“…The coordination at gold is quasi linear (C1–Au–C6 = 177.4(4)°), and the Au–C distances are found to be 2.017(9) and 2.025(9) Å. These values are similar to those reported in the literature for related gold compounds. − The pyridine rings are tilted 19° with respect to each other. In general, the value of this angle has been reported to be less than 10° for bis-perfluorinated derivatives except in the case of the tetrabutylammonium derivative NBu 4 [Au(C 6 F 5 ) 2 ] and the closely related silver compound PNP[Ag(C 6 F 4 N) 2 ], where this angle is ca.…”

Section: Resultssupporting

confidence: 81%

Design and Synthesis of Polytopic Metalloligands Based on Fluoroaryl Gold(I) Organometallic Compounds

Ferrer¹,

Gutiérrez²,

Mounir³

et al. 2011

Organometallics

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b S Supporting Information ' INTRODUCTIONThe design and synthesis of supramolecular self-organized systems with specific properties and functions in order to obtain advanced materials has increased in recent years. In particular, noteworthy advances have occurred in the field of engineering crystalline materials built from selected molecular components. 1À5 Molecular subunits are particularly effective when they incorporate multiple sites in particular orientations that favor the selfassembly of the building blocks to yield the predesigned supramolecular species.While most metalÀorganic systems have been synthesized directly from metal ions and organic ligands, the "complex as ligand" or "metalloligand" strategy, i.e., the use of metal complexes with "free" donor groups for further metal bonding as synthetic precursors, has also been developed. 6À11 Such ligands are the basis for the preparation of multinuclear complexes and coordination arrays of various dimensionalities. Conceptually, in an expanded ligand the spacer groups introduced are replaced by metal-containing moieties.The use of metallic complexes as building block precursors has proved to be a very useful strategy for the design and syntheses of ABSTRACT: New neutral and anionic fluoroaryl gold(I) complexes featuring terminal pyridine rings were prepared following different strategies. The homoleptic anionic compounds NBu 4 -[Au(C 5 F 4 N) 2 ] (1) and NBu 4 [Au(C 6 F 4 py) 2 ] (2) were obtained by reacting [AuCl(tht)] (tht = tetrahydrothiophene) with the organolithium derivatives of BrC 5 F 4 N and BrC 6 F 4 py, respectively. This route required the previous synthesis of the new fluorinated compound BrC 6 F 4 py, which was produced by a Stille cross-coupling between (4-pyridyl)trimethylstannane and 1,4-dibromotetrafluorobenzene. The neutral phosphane compounds [Au(C 6 F 4 N)(PPh 3 )] (3) and [Au(C 6 F 4 py)(PPh 3 )] (4) were obtained by treatment of [AuCl(PPh 3 )] with the organolithium reagents LiC 6 F 4 N and LiC 6 F 4 py, respectively. However, this synthetic strategy failed for organogold compounds containing a polyphosphane ligand. Consequently, an alternative synthetic procedure, based on displacement reactions of the weakly coordinated tht ligand from [Au(C 6 F 4 py)(tht)] by the appropriate polyphosphane, was undertaken. Thus, the following complexes were isolated and characterized: [(AuC 6 F 4 py) 2 (μ 2 -diphosphane)] [diphosphane = bis(diphenylphosphanyl)methane (dppm) (9), 2,2-bis(diphenylphosphanyl)propane (dppip) (10), 1,2-bis(diphenylphosphanyl)ethane (dppe) (11), trans-1,2-bis-(diphenylphosphanyl)ethylene (dppet) (12), 1,2-bis(diphenylphosphanyl)acetylene (dppa) (13), 1,3-bis(diphenylphosphanyl)-propane (dppp) (14), 1,4-bis(diphenylphosphanyl)butane (dppb) (15), 4,4 0 -bis(diphenylphosphanyl)-1,1 0 -biphenyl (dppdph) (16)], [(AuC 6 F 4 py) 3 (μ 3 -triphosphane)] [triphosphane = 1,1,1-tris(diphenylphosphanylmethyl)ethane (triphos) (17), 1,3,5-tris(diphenylphosphanyl)benzene (triphosph) (18)], and [(AuC 6 F 4 py) 4 (μ 4 -tetraphosphane)] ...

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Section: Resultssupporting

confidence: 81%

Design and Synthesis of Polytopic Metalloligands Based on Fluoroaryl Gold(I) Organometallic Compounds

Ferrer¹,

Gutiérrez²,

Mounir³

et al. 2011

Organometallics

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“…Surprisingly, the electrochemical behavior corresponds to a reversible single-electron transfer process and indicates that this gold(III) can be reduced to gold(II) and that the gold(II) state has reasonable stability on the electrochemical time scale [340]. The reaction of this complex with 2 equivalents of [Au(C 6 F 5 )(tht)] gives [Au{PPh 2 C(PPh 2 Me)C(SAuC 6 F 5 )S} 2 ] þ (Figure 1.73c), which is a vapochromic material and can be used for the detection of some volatile organic compounds [341]. The reaction of this complex with 2 equivalents of [Au(C 6 F 5 )(tht)] gives [Au{PPh 2 C(PPh 2 Me)C(SAuC 6 F 5 )S} 2 ] þ (Figure 1.73c), which is a vapochromic material and can be used for the detection of some volatile organic compounds [341].…”

Section: Gold(iii) Complexes With Chalcogen Ligandsmentioning

confidence: 99%

The Chemistry of Gold

Gimeno

2008

Modern Supramolecular Gold Chemistry

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“…, resulting from a carbon-carbon coupling reaction, is obtained. 11 The reaction of methylene active compounds with CS 2 and LiNR 2 , NaH, 12 or K 2 CO 3 , 13 led to the synthesis of the corresponding 2,2-disubstituted ethylene-1,1-dithiolate salts, which were treated in situ with MeI to give ketene dithioacetals. In this context acetylacetone has been used to prepare the 2-acetyl-2-oxopropylidene-S,S-acetal [13][14][15] Our synthetic method is, therefore, unprecedented.…”

mentioning

confidence: 99%

CS2 insertion into a gold–carbon bond. First syntheses and characterization of 2,2-diacetylethylene-1,1-dithiolato complexes. Crystal structure of [N(PPh3)2][Au{η2-S2CC(COMe)2}2]†

Vicente¹,

Chicote²,

González‐Herrero³

et al. 1997

Chem. Commun.

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Carbon−Carbon Coupling via Nucleophilic Addition of a Gold(I) Methanide Complex to Heterocumulenes

Cited by 15 publications

References 24 publications

Design and Synthesis of Polytopic Metalloligands Based on Fluoroaryl Gold(I) Organometallic Compounds

Design and Synthesis of Polytopic Metalloligands Based on Fluoroaryl Gold(I) Organometallic Compounds

The Chemistry of Gold

CS2 insertion into a gold–carbon bond. First syntheses and characterization of 2,2-diacetylethylene-1,1-dithiolato complexes. Crystal structure of [N(PPh3)2][Au{η2-S2CC(COMe)2}2]†

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