A Helical Metal−Metal Bonded Chain via the Pt→Ag Dative Bond

Yamaguchi, Tadashi; Yamazaki, Fumie; Ito, Tasuku

doi:10.1021/ja002906a

Cited by 117 publications

(111 citation statements)

References 18 publications

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“…Such donating property of dialkyl-or diarylplatinum was already used for constructing heterometal clusters. 60 We found that reduction of [ 4 ] in THF, in consistent with the observed complexation of the molybdenum analogs. Complexes 53 and 54 were not isolated and accordingly characterized by only spectroscopic methods.…”

Section: 84supporting

confidence: 83%

Linearly Aligned Metal Clusters: Versatile Reactivity and Bonding Nature of Tetrametal M–Mo–Mo–M Complexes (M = Pt, Pd, Ir, and Rh) Supported by 6-Diphenylphosphino-2-pyridonato Ligand

Mashima¹

2010

Bulletin of the Chemical Society of Japan

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A tridentate ligand, pyphos (6-diphenylphosphino-2-pyridonato), was utilized to prepare tetrametal complexes since this ligand has unique coordinating sites comprised of three different elements, i.e., phosphorus, nitrogen, and oxygen, in almost linear fashion. By using pyphos ligand, linearly aligned tetrametal complexes of group 10 metals [Mo 2 M 2 -(pyphos) 4 X 2n ] (M = Pt and Pd; n = 0, 1, and 2) were prepared, and for group 9 metals, [Mo 2 M 2 (pyphos) 4 (RNC) 4

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Section: 84supporting

confidence: 83%

Linearly Aligned Metal Clusters: Versatile Reactivity and Bonding Nature of Tetrametal M–Mo–Mo–M Complexes (M = Pt, Pd, Ir, and Rh) Supported by 6-Diphenylphosphino-2-pyridonato Ligand

Mashima¹

2010

Bulletin of the Chemical Society of Japan

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“…[4,25] A less common binding mode shows additional interaction of the acidic metal with one or two of the ligand atoms directly attached to platinum. [15,17,19,[26][27][28] This latter kind of interaction resembles that occurring in most of the key intermediate species proposed in heterobimetallic catalysis. In this communication we report the synthesis and characterization of a rare heterobimetallic Pt-Au complex having an unusual metal-metal bonding mode and a surprising dynamic behaviour in solution.…”

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confidence: 65%

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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“…Metal-metal bonds can act as a link between different subassemblies, making them a valuable tool in molecular or crystal engineering, and giving rise to a variety of structures, from simple linear bimetallic compounds to infinite one-dimensional chains [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30]. Furthermore, some of these complexes show interesting photophysical and photochemical properties [1][2][3][4][5]7,8,11,17,27,[29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48], which in some cases have been exclusively attributed to the presence...…”

Section: Introductionmentioning

confidence: 99%

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Baya

Belío

Forniés

et al. 2015

Inorganica Chimica Acta

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Luminescent complexes a b s t r a c t Complexes [Pt(C 6 F 5 )(bzq)(CNR)] {R = t Bu (1), 2-naphthyl (2), 2,6-Me 2 Ph (3)} have been prepared by replacement of the labile acetone in [Pt(C 6 F 5 )(bzq)(Me 2 CO)] with the corresponding isocyanide ligand. The structures 1 and 3 (X-ray) confirms their square planar geometry, with the bzq ligand coplanar to the metal plane. The reactions of 1-3 toward AgClO 4 lead to the trinuclear complexes [{Pt(C 6 F 5 ) (bzq)(CNR)} 2 Ag]ClO 4 {R = t Bu (4), 2-naphthyl (5)} or the tetranuclear [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6). The structures of these three polynuclear complexes have been established by X-ray diffraction studies. Two pseudo-polymorphs of 4 (4a and 4b), only differing in the crystallization solvent, have been found. 4a/b and 5 are trinuclear Pt-Ag-Pt complexes with a ''sandwich'' disposition. In all three cases, two ''Pt(C 6 F 5 )(bzq)(CNR)'' fragments are linked by a silver atom through Pt ? Ag bonds of donor acceptor nature and the silver center establishes a short g 1 interaction with the C ipso of the bzq ligands. Furthermore, the study of the structure of 6 reveals two ''(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph)PtAg'' subunits, each containing a Pt ? Ag bond related by an inversion center and held together through g 2 interactions established by the silver atom of one unit and one of the aromatic rings of the bzq ligand of the other. The reaction of 1-3 with [Ag(OClO 3 )(PPh 3 )] produces [(C 6 F 5 )(bzq)(CNR)PtAg(PPh 3 )]ClO 4 {R = t Bu, (7), 2-naphthyl (8), 2,6-Me 2 Ph (9)}. These dinuclear clusters contain a Pt ? Ag bond and show dynamic processes in solution (NMR) which involve the rupture and formation of these interactions. The X-ray structure of 7 confirms the presence of a Pt-Ag bond and a g 1 interaction with the C ipso of the bzq ligand (2.514(6) Å). All the crystal structures determined show pÁ Á Áp interactions of the bzq which stack in a parallel fashion with interplanar distances of ca. 3.3-3.4 Å. In 5 and 6 the aromatic fragments of the isocyanide ligands also take part in these pÁ Á Áp interactions. Absorption and emission properties of all the complexes 1-9 have been studied and explained with the aid of TD-DFT theoretical calculations.Compounds 1-9 are not emissive in solution but they are in rigid matrix. In glassy 2-Me-THF or CH 2 Cl 2 at 77 K the Pt/Ag compounds 4-9 at any concentration (10 À3 M, 10 À4 M, 10 À5 M) show the same emission spectra as their corresponding starting complexes 1-3, in line with the rupture of the Pt-Ag bonds. In the solid state only the dinuclear compounds [Pt(C 6 F 5 )(bzq)(CN-t Bu)AgPPh 3 ]ClO 4 (7) and [Pt(C 6 F 5 )(bzq) (CN-2,6-Me 2 Ph)AgPPh 3 ]ClO 4 (9) together with the tetranuclear complex [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6) are emissive at room temperature showing bright greenish (7, 9) or yellowish (6) phosphorescence. In all three compounds a significant contribution of M 0 orbitals (AgPPh 3 /Ag) to the frontier orbitals (FO) has been observed, and their main emissions see...

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A Helical Metal−Metal Bonded Chain via the Pt→Ag Dative Bond

Cited by 117 publications

References 18 publications

Linearly Aligned Metal Clusters: Versatile Reactivity and Bonding Nature of Tetrametal M–Mo–Mo–M Complexes (M = Pt, Pd, Ir, and Rh) Supported by 6-Diphenylphosphino-2-pyridonato Ligand

Linearly Aligned Metal Clusters: Versatile Reactivity and Bonding Nature of Tetrametal M–Mo–Mo–M Complexes (M = Pt, Pd, Ir, and Rh) Supported by 6-Diphenylphosphino-2-pyridonato Ligand

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

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

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