Synthesis of Pentafluorophenyl Silver by Means of Lewis Acid Catalysis: Structure of Silver Solvent Complexes

Kuprat, Marcus; Lehmann, Mathias; Schulz, Axel; Villinger, Alexander

doi:10.1021/om901063a

Cited by 99 publications

(106 citation statements)

References 55 publications

Supporting

Mentioning

100

Contrasting

Order By: Relevance

“…This interaction seems similar in nature to those described for 4 and 5, and to other similar sandwich complexes [13,[26][27][28]30] but in the case of 6 the shorter Ag-C distance (2.433(3) Å) corresponds to the carbon atom adjacent to the bzq C ipso (C(16)), also with a relatively short distance involving this C ipso (C(17), 2.516(3) Å). These structural parameters seem to point in this case to a di-hapto Agbzq interaction, a common feature found for complexes containing silver and aromatic rings [12,[70][71][72]. The absence of a second PtAg bond for the silver center could be responsible for this di-hapto configuration versus the mono-hapto found in the trinuclear sandwich complexes.…”

Section: Reactivity Of 1-3 Toward Agclomentioning

confidence: 64%

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

View full text Add to dashboard Cite

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...

show abstract

Section: Reactivity Of 1-3 Toward Agclomentioning

confidence: 64%

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

View full text Add to dashboard Cite

show abstract

“…NaN 3 (99 %, Acros) was used as received. Silver trifluoromethylsulfonate (AgOTf), [43] dichloro-[(2,4,6-tri-tert-butylphenyl)(trimethylsilyl)amino]stibane (Mes*N-(SiMe 3 )SbCl 2 , 1), [(2,4,6-tri-tert-butylphenyl)(trimethylsilyl)amino]-bis(trifluoromethylsulfonyl)stibane (Mes*N(SiMe 3 )Sb(OTf) 2 , 2), [7] and B(C 6 F 5 ) 3 [44] were prepared according to literature procedures. X-ray Structure Determination: X-ray-quality crystals of 2, 3, 3·toluene, 4, 5, 6, 9a, 9b, and 10 were selected in Kel-F-oil (Riedel deHaen) or Fomblin YR-1800 (Alfa Aesar) at ambient temperatures.…”

Section: Methodsmentioning

confidence: 99%

Syntheses, Structure, and Reactivity of Amino(azido)stibanes

2012

Self Cite

View full text Add to dashboard Cite

Amino(azido)stibanes Mes*N(SiMe 3 )Sb(N 3 )X (X = N 3 , Cl, OTf) were synthesized and fully characterized. Their structures were determined by single-crystal X-ray diffraction and are rare examples of antimony azides. On account of weak Sb···X van der Waals interactions, centrosymmetric dimers are observed in the solid state. Mes*N(SiMe 3 )Sb(OTf)X species (X = Cl, N 3 , and OTf; OTf = triflate = CF 3 SO 3 -) are labile

show abstract

“…Neat AgC 6 F 5 . As illustrated in Scheme 2,5 solvent-free, pure AgC 6 F 5 was obtained from Li[B (C 6 F 5 ) 4 ] and AgF, which were first combined and suspended in dichloromethane prior to sonification in an ultrasonic bath at 40−60°C for 8 h. The resulting grayish suspension was filtered, resulting in a clear, brownish solution. Removal of CH 2 Cl 2 followed by extraction of B(C 6 F 5 ) 3 by washing with n-hexane yielded an offwhite solid AgC 6 F 5 (yield: 90%, T dec = 276°C).…”

Section: H 5 N) 3 ][Aumentioning

confidence: 99%

Pentafluorophenyl Silver: Structure and Bonding of Arene Solvates

Schulz

Villinger

2015

Organometallics

Self Cite

View full text Add to dashboard Cite

The synthesis and full characterization of a series of AgC 6 F 5 ·arene complexes (arene = RC 6 H 5 with R = Me, Et; R 2 C 6 H 4 , R 3 C 6 H 3 , R 4 C 6 H 2 , and R 5 C 6 H with R = Me) are presented. The structure and bonding are discussed on the basis of X-ray and theoretical studies with respect to the substitution pattern at the arene. Additionally, the structure of neat AgC 6 F 5 and a facile way to generate crystals of pure AgC 6 F 5 are reported.

show abstract

Synthesis of Pentafluorophenyl Silver by Means of Lewis Acid Catalysis: Structure of Silver Solvent Complexes

Cited by 99 publications

References 55 publications

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

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

Syntheses, Structure, and Reactivity of Amino(azido)stibanes

Pentafluorophenyl Silver: Structure and Bonding of Arene Solvates

Contact Info

Product

Resources

About