Complexes with platinum-gold and -silver bonds: catalysis by silver(I) of alkyl exchange reactions between platinum centers

Arsenault, Gilles; Anderson, Craig M.; Puddephatt, Richard J.

doi:10.1021/om00100a002

Cited by 61 publications

(53 citation statements)

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“…As anticipated by 31 P NMR data analysis of complex 5 (see below), the dppy ligand in 5 swapped in comparison with that observed in 1e4 in which the nitrogen atom of dppy ligand coordinated to platinum center and consequently, coordination to gold center now occurs through the P atom of the dppy ligand. The crystal structure of complex 5 reveals a slightly distorted square planar geometry about the Pt(II) center with C(1)-Pt(1)-N(1) and C(10)-Pt(1)-N(2) angles of 171.9(1) and 176.58 (9) , respectively. The Pt-Au vector is tilted by 10.28(6) with respect to the normal line of the platinum coordination plane and the dihedral angle P(1)-Au(1)-Pt(1)-N(2) is À23.33 (5) .…”

Section: Synthesis and Structuresmentioning

confidence: 99%

“…The 31 P NMR spectrum of complex 5 ( As summarized in Scheme 1, reaction of 1 with 1 equiv AuCl(SMe 2 ) in acetone at À60 C (to prevent oxidative-addition of Au-Cl bond to 1) [9] gave the heterobinuclear complex [PtMe(bhq) (m-dppy)AuCl], 8, in good yield by replacement of the SMe 2 ligand with the P ligating atom of dppy. Complex 8 is a yellow solid that is stable in acetone solution for several hours and fully characterized by NMR spectroscopy and microanalysis and its structure in the solid state determined using X-ray crystallography.…”

Section: Synthesis and Structuresmentioning

confidence: 99%

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Synthesis and structure of the cyclometalated hetero-binuclear Pt-Au complexes with bridging 2-diphenylphosphinopyridine ligand

Karimi

Jamali

2015

Journal of Organometallic Chemistry

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Section: Synthesis and Structuresmentioning

confidence: 99%

Section: Synthesis and Structuresmentioning

confidence: 99%

Synthesis and structure of the cyclometalated hetero-binuclear Pt-Au complexes with bridging 2-diphenylphosphinopyridine ligand

Karimi

Jamali

2015

Journal of Organometallic Chemistry

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“…[6,7] Thei nterest in these systems has increased lately because species containing such interactions play acentral role in cooperative catalysis. [8] Forexample,complexes with PtÀAu,Pt ÀCu, or PtÀAg bonds have been identified in the gas phase or in solution as intermediates in transmetalation reactions involving methyl groups, [9][10][11] whereas Pd À Au or Pd À Cu species have been proposed as transition states in aryl-ligand-interchange processes. [12,13] However,scarce experimental evidence for intermediates of this kind has been provided, and the nature and properties of these intermediates remains unexplored so far.…”

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confidence: 99%

Unusual Metal–Metal Bonding in a Dinuclear Pt–Au Complex: Snapshot of a Transmetalation Process

et al. 2016

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The dinuclear Pt-Au complex [(CNC)(PPh 3 )PtAu(PPh 3 )](ClO 4 ) (2) (CNC = 2,6-diphenylpyridinate) has been prepared. Its crystal structure shows a rare metal-metal bonding situation, with very short Pt-Au and Au-C ipso (CNC) distances and dissimilar Pt-C ipso (CNC) ) is a field which is attracting a considerable attention in chemistry. These interactions have proven to be a powerful tool for crystal engineering, [1][2][3][4][5] and the complexes containing them show interesting photophysical and photochemical properties related to the occurrence of M-M bonds. [6, 7] Besides, the interest on these systems has increased lately because species containing this kind of interactions play a central role in cooperative catalysis. [8] For example, complexes with Pt-Au, Pt-Cu or Pt-Ag bonds have been identified in either gas phase or in solution as intermediates in transmetalation reactions involving methyl groups, [9][10][11] whereas Pd-Au or Pd-Cu species have been proposed as transition states in aryl ligand interchange processes. [12, 13] [8]The M-M interactions described above are of dative nature and are established between a basic donor metallic center and an acidic acceptor metal. A number of metals are known to fulfill this role but Pt II (d 8 ) is the donor center par excellence, [1, 4,9,[14][15][16][17][18] while among the acceptors, Ag) is by far the most representative example. [19,20] In [29] with PPh 3 . The crystal structure of 1 has been determined by X-ray diffraction and shows the expected square planar coordination around the platinum (see Figure S3 and Table S1 The crystal structure of 2 has been determined by X-ray diffraction (see Figure 1, and a selection of relevant bond distances and angles is included in the caption. ; R = PPh 3 , X = Cl, 2.792(1) Å). Supporting Information for details). A drawing of its complex cation is shown in[23] Moreover, a striking feature of 2 is the interaction between the Au center and the ipso carbon of one of the phenylene rings of the CNC ligands. Thus, the Au-C7 distance is intriguingly short. Concomitantly, the Pt-C7 distance becomes significantly longer than the Pt-C13 one, the later being in the typical range found for Pt(II) complexes containing this or quite similar CNC ligands. [15, 16,31,32] The C7 phenylene ring remains perfectly planar. However, while the rest of the CNC ligand remains coplanar with the square planar environment of the Pt center, the C7 ring remarkably deviates from this plane (23.1(1)º).The bonding situation involving Pt, Au and C7 atoms found in the solid state for 2 does not to fit into the traditional model of square planar Pt(II)→M donor acceptor complexes. Thus, the Pt-Au line deviates considerably from the perpendicular to the Pt-N-C13 plane and the Pt-Au-P2 line bends 152.38(2)º), with the result of the Au atom leaning towards C7 (Au-Pt-C 7 angle of 52.7(1)º). This kind of situation, although reported in some examples, [9, 15] remained unstudied so far.[33] in complex 2 can be gained by means of the EDA-N...

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“…Besides, formation of R–AuPPh 3 (path b, Scheme ) could also be ruled out, as the signal for the gold–phosphine bond is not expected to change so dramatically . Alternatively, the chemical shift of the Ph 3 P in a [Pt]–AuPPh 3 complexes has been reported to appear at ≈4 ppm, supporting a (L)Cl n Pt–AuPPh 3 cluster complex as the homogeneous active catalytic species for the isomerisation and second nucleophilic attack with both nucleophiles (cycles 2 and 3, Scheme )…”

Section: Resultsmentioning

confidence: 99%

Evidence of Hybrid Homogeneous–Heterogeneous Catalysis in a Pt/Au Heterobimetallic System

Alonso

Muñoz

2018

ChemCatChem

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We report here our efforts towards understanding the catalytic species involved in a novel Pt/Au heterobimetallic system capable of efficiently catalysing the tandem cyclisation/C−X coupling reaction of heteroarylallenes with C‐ and N‐based nucleophiles. Our results confirm that homogeneous Au‐catalysis is involved at the beginning of the reaction to generate an intermediate that enters the second catalytic cycle in which hybrid homogeneous–heterogeneous catalysis by [Pt–Au] clusters could be responsible for the high efficiency. In this part of the cycle, [Pt–AuPPh3] homogeneous clusters (identified by 31P NMR analysis) seem to be aided by Pt–Au particles in the heterogeneous phase (supported by Hg poisoning, filtration experiments and characterisation of the possible catalytic species by several techniques, such us 31P NMR spectroscopy, inductively coupled plasma mass spectrometry, SEM and dynamic light scattering experiments). Here, full Pt‐to‐Au transmetallation was not observed contrary to the results with other bimetallic systems. Although a few examples of hybrid homogeneous–heterogeneous catalysis in monometallic systems exist, to the best of our knowledge, this is the first example of hybrid homogeneous–heterogeneous catalysis in systems involving two different metals.

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Complexes with platinum-gold and -silver bonds: catalysis by silver(I) of alkyl exchange reactions between platinum centers

Cited by 61 publications

References 4 publications

Synthesis and structure of the cyclometalated hetero-binuclear Pt-Au complexes with bridging 2-diphenylphosphinopyridine ligand

Synthesis and structure of the cyclometalated hetero-binuclear Pt-Au complexes with bridging 2-diphenylphosphinopyridine ligand

Unusual Metal–Metal Bonding in a Dinuclear Pt–Au Complex: Snapshot of a Transmetalation Process

Evidence of Hybrid Homogeneous–Heterogeneous Catalysis in a Pt/Au Heterobimetallic System

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