Luminescent gold(I) macrocycles with diphosphine and 4,4′-bipyridyl ligands

Brandys, Marie-Claude; Jennings, Michael C.; Puddephatt, Richard J.

doi:10.1039/b005251p

Cited by 204 publications

(180 citation statements)

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“…17 However, this is not true in all cases and the recent report by the same group has shown that ligands of the type Ph2P(CH2)nPPh2 (n = 1, 3 or 5) prefer to form tetranuclear macrocycles instead of polymeric chains. 18 This leads to the conclusion that the steric/electronic effects may not play any role in the formation of a particular complex. Instead, both the macrocyclic and the polymeric complexes could exist in a rapid equilibrium in solution with the least soluble complex preferentially crystallizing or precipitating from the solution.…”

Section: Resultsmentioning

confidence: 99%

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Bi-, Tetra-, and Hexanuclear Au^I and Binuclear Ag^I Complexes and Ag^I Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC₆H₄OMe-o)₂}₂, and Pyridyl Ligands

et al. 2008

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The reactions of phenylaminobis(phosphonite), PhN{P(OC6H4OMe-o)2}2 (1) (PNP) with [AuCl(SMe2)] in appropriate ratios, afford the bi-, and mononuclear complexes, 3 IntroductionFor the past few decades there has been continued interest in the chemistry of d 10 metal systems due to the rich photochemical properties, 1 catalytic applications, 2 and use in drug discovery. 3 In addition to a variety of coordination geometries, the short metalmetal contacts, described as "metallophilicity", have been employed in the construction of several macrocyclic molecules and supramolecular architectures via intra-and intermolecular aggregations. 4 The term "aurophilicity" has been introduced to describe The 31 P NMR spectrum of 2 consists of a single peak at 114.3 ppm whereas 3 shows two doublets centered at 112.2 and 133.8 ppm, with a large 2 JPP coupling of 341 Hz. 16 The 1 H NMR spectra of 2 and 3 show single resonances corresponding to the ortho-methoxy groups at 3.82 and 3.71 ppm, respectively. The structure of complex 2 was confirmed by an X-ray structure determination. 6Bi-, tetra-and hexanuclear Au I macrocycles. Complex 2 is a potential precursor for the preparation of various bi-, tetra-and hexanuclear gold(I) macrocycles due to the presence of two highly polar Au-Cl bonds. ligands, we believe that the "rigid short-bite" R2PN(R')PR2 (where R, R' = alkyl or aryl)ligands with bulky substituents around the phosphorus centers will prefer to form thermodynamically favored ring structures instead of forming the polymers. Although these complexes are moderately stable to air, they turn purple after keeping for a long time even under inert atmosphere. Silver(I) DerivativesThe reaction of 1 with AgOTf in a 1:2 mole ratio leads to the formation of a binuclear complex, [Ag2(μ-OTf)2(μ-PNP)] (9), in quantitative yield. In complex 9, the Ag I atoms are bridged by a pair of trifluoromethanesulfonate ions and a PNP ligand so as to provide trigonal planar geometry around the Ag I centers. The displacement of trifluoromethanesulfonate ligands in 9 by two equivalents of 1 afforded a "manxane"-like triply-bridged binuclear complex, [Ag2(μ-PNP)3](OTf)2 (10) as shown in Scheme 3. The 31 P NMR spectrum of complex 9 consists of the A portion of a AA'XX' multiplet centered at 116.7 ppm, whereas the resonance due to 10 appears at 120.8 ppm as a broad singlet. 20The complex, [Ag2(C4H8O)2(µ-PNP)2](ClO4)2 (11) has been prepared by reacting equimolar amount of 1 with AgClO4 in THF. In the 31 P NMR spectrum of complex 11, the resonance appears at 109.2 ppm as a broad doublet due to the complex spin system. In the 1 H NMR spectrum, the resonances corresponding to the coordinated THF molecules appear as two triplets centered at 1.84 and 3.73 ppm with an apparent JHH coupling of 3.6 Hz. The resonance due to the ortho-methoxy and aromatic protons appear in the appropriate regions with the expected relative intensities. Although, the 91 JAgP values for complexes 9 -11 are significantly larger than that observed in analogous phosphine systems, the ...

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Section: Resultsmentioning

confidence: 99%

“…All the solvents were purified by conventional procedures and distilled prior to use. 25 The compounds PhN{P(OC6H4OMe-o)2}2 14e and AuCl(SMe2) 18 were prepared according to the published procedures. AgX (X = OTf and ClO4), pyrazine, 1,3,5-triazine, 2,2'-bipyridine and 4,4'-bipyridine were purchased from Aldrich chemicals and used as such …”

Section: Methodsmentioning

confidence: 99%

Bi-, Tetra-, and Hexanuclear Au^I and Binuclear Ag^I Complexes and Ag^I Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC₆H₄OMe-o)₂}₂, and Pyridyl Ligands

et al. 2008

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“…5 and Supplementary Discussion) 22,23 . X-ray Diffraction together with cyclic voltammetry studies showed that while 5a presents aurophilic bonding between two gold atoms 14 , 5c has no aurophilic bonds at all 14 and 5b has an intermediate behaviour, depending on the counteranion 24,25 . The results indicate that aurophilic bonding has a positive influence on the reaction rate but none on the distal size selectivity.…”

Section: Resultsmentioning

confidence: 99%

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

2015

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Metal-catalysed chemical reactions are often controlled by steric hindrance around the metal atom and it is rare that substituents far away of the reaction site could be differentiated during reaction, particularly if they are simple alkyl groups. Here we show that a gold catalyst is able to discriminate between linear carbon alkynes with 10 or 12 atoms in the chain during the oxidative homocoupling of alkynes: the former is fully reactive and the latter is practically unreactive. We present experimental evidences, which support that the distal size selectivity occurs by the impossibility of transmetallating two long alkyl chains in an A-framed, mixedvalence digold (I, III) acetylide complex. We also show that the reductive elimination of two alkyne molecules from a single Au(III) atom occurs extremely fast, in o1 min at À 78°C (turnover frequency40.016 s À 1 ).

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“…[(t-Bu 3 P) 2 Pt], PPh 3 , and NaBF 4 were purchased from commercial sources, and AuCl(SMe 2 ) and AuCl(PPh 3 ) were prepared as described previously [10,11]. Crystal data and re nement parameters for 5 are given in Table 2.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of a new T-shaped heterobinuclear Pt0-AuI complex [(t-Bu3P)2PtAu(PPh3)]BF4 from trinuclear gold cluster complex [(PPh3)Au]3(-O)BF4

2016

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Luminescent gold(I) macrocycles with diphosphine and 4,4′-bipyridyl ligands

Cited by 204 publications

References 22 publications

Bi-, Tetra-, and Hexanuclear Au^I and Binuclear Ag^I Complexes and Ag^I Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC₆H₄OMe-o)₂}₂, and Pyridyl Ligands

Bi-, Tetra-, and Hexanuclear Au^I and Binuclear Ag^I Complexes and Ag^I Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC₆H₄OMe-o)₂}₂, and Pyridyl Ligands

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

Synthesis of a new T-shaped heterobinuclear Pt0-AuI complex [(t-Bu3P)2PtAu(PPh3)]BF4 from trinuclear gold cluster complex [(PPh3)Au]3(-O)BF4

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Luminescent gold(I) macrocycles with diphosphine and 4,4′-bipyridyl ligands

Cited by 204 publications

References 22 publications

Bi-, Tetra-, and Hexanuclear AuI and Binuclear AgI Complexes and AgI Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC6H4OMe-o)2}2, and Pyridyl Ligands

Bi-, Tetra-, and Hexanuclear AuI and Binuclear AgI Complexes and AgI Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC6H4OMe-o)2}2, and Pyridyl Ligands

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

Synthesis of a new T-shaped heterobinuclear Pt0-AuI complex [(t-Bu3P)2PtAu(PPh3)]BF4 from trinuclear gold cluster complex [(PPh3)Au]3(-O)BF4

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Bi-, Tetra-, and Hexanuclear Au^I and Binuclear Ag^I Complexes and Ag^I Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC₆H₄OMe-o)₂}₂, and Pyridyl Ligands

Bi-, Tetra-, and Hexanuclear Au^I and Binuclear Ag^I Complexes and Ag^I Coordination Polymers Containing Phenylaminobis(phosphonite), PhN{P(OC₆H₄OMe-o)₂}₂, and Pyridyl Ligands