Gold Chemistry Guided by the Isolobality Concept<sup>†</sup>

Raubenheimer, Helgard G.; Schmidbaur, Hubert

doi:10.1021/om2010113

Cited by 124 publications

(145 citation statements)

References 214 publications

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“…It has been demonstrated that Au…π(arene) interactions occur in both neutral and charged gold(I)-and gold(III)-containing molecules and it has been estimated that when they potentially can form are found in approximately 2 % of their structures. To a first approximation, the nature of the interaction can be described as electron donation from the aromatic ring to the gold atom, akin to the C-H…π(arene) interactions and in accord with the isolobal analogy between gold and hydrogen [48]. This being the case, it might be anticipated that increasing the electron density of the aromatic ring, say, by the incorporation of a nitrogen atom, should enhance the propensity of forming such interactions and their strength.…”

Section: Intermolecular Au…π(arene) Interactionsmentioning

confidence: 99%

Supra-molecular synthons based on gold…π(arene) interactions

2013

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Section: Intermolecular Au…π(arene) Interactionsmentioning

confidence: 99%

Supra-molecular synthons based on gold…π(arene) interactions

2013

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“…[35] DFT modelling of this process supports this proposal and estimates an activation barrier of 8.9 kcal/mol (see Supporting Information). + fragment and a proton [36] suggests that 2 can be alternatively viewed as a model for a frozen intermediate of the protonation of a Pt(II)-R species, [37] a very relevant process in connection with the functionalization of hydrocarbons by Pt complexes. [38] In conclusion, we report herein a novel heterobimetallic complex that exhibits a peculiar bonding situation involving Pt-Au and Au-C bonds.…”

mentioning

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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“…This work has been extended as shown here. The present communication is also an addition to the discussion of the isolobality concept [9] …”

Section: Introductionmentioning

confidence: 88%

“…Owing to the C 3v symmetry, the dihedral angle H-P-B-Au of 60.0 • indicates a perfectly staggered conformation, and the dihedral angle H-P-(Au)-B-P shows that there is no distortion away from an eclipsed conformation of the units under consideration. 3 PAu] + , the relation to simple phosphine-boranes R 3 PBH 3 is also obvious [9].…”

Section: The Calculated Structure Of the Model System H 3 Pb[au(phmentioning

confidence: 94%

“…This work has been extended as shown here. The present communication is also an addition to the discussion of the isolobality concept [9] which relates [LAu] + cations with the proton H + (L = donor ligand), and thus the title compound with the simple phosphine borane Cy 3 PBH 3 . This communication has prompted us to report on details of an earlier synthesis of the title trinuclear gold compound (2, Scheme 1) which have never been fully disclosed.…”

Section: Introductionmentioning

confidence: 94%

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