Cyclic silver(I) compounds having a [mu-(Bzim)Ph2PAg](2)(2+) unit ((Bzim)Ph2P 1-benzyl-2-imidazolyldiphenylphosphine) and NO3- (I), BF4- (II), and B[3,5-(CF3)(2)C6H3](4)(-) (III) as counterions were characterized in the solid state by X-ray crystal structure determinations (I, II), and in solution by H-1-, C-13-, F-19- and P-31-NMR spectroscopies. The crystal structure of complex [mu-(Bzim)Ph2PAg(NO3)](n) (n = 2, 4) (I) (triclinic, space group (no. 2), a = 15.118(5), b = 17.755(3), c = 14.123(4) Angstrom, alpha = 90.23(2), beta = 111.67(2), gamma = 85.92(2)degrees, Z = 2) shows two conformers A and B in the unit cell. The conformer A consists of a tetranuclear species formed by two [mu-(Bzim)Ph2PAg](2)(2+) moieties, related by a center of symmetry, bonded together by two bridging nitrate anions. The nitrate anions are coordinated to the sliver atoms in an unusual fashion. The conformer B is a dinuclear species where the silver atoms present in the eight-membered ring complete their tetracoordination with two chelate nitrate anions. The crystal structure of complex {[mu-(Bzim)Ph2PAg(BF4)](2)}(infinity) (II) (monoclinic, space group P2(1)/c (no. 14), a = 11.563(3), b = 8.353(4), c = 26.188(7) Angstrom, beta = 95.88(2)degrees, Z = 2) consists of infinite chains of the dinuclear cyclic silver moieties held together by BF4- bridging anions. The low temperature experimental and simulated P-31-NMR spectra of complexes I-III show complex apparent doublets of multiplets due to the resonance of the spin systems of the three isotopomers of the silver atoms present in the cyclic units. The interionic solution structure of complex II was investigated by F-19{H-1}-HOESY NMR spectroscopy. In methylene chloride solution the BF4- anion is not more coordinated to the silver(I) atoms as in the solid state, and it is localized in between the phenyl and benzyl groups of the ligand. (C) 2000 Elsevier Science S.A. All rights reserved.

Solid state and solution structural studies of silver(I) cyclic complexes bearing the (Bzim)Ph2P ligand

Burini, A
;
Galassi, R;
2000-01-01

Abstract

Cyclic silver(I) compounds having a [mu-(Bzim)Ph2PAg](2)(2+) unit ((Bzim)Ph2P 1-benzyl-2-imidazolyldiphenylphosphine) and NO3- (I), BF4- (II), and B[3,5-(CF3)(2)C6H3](4)(-) (III) as counterions were characterized in the solid state by X-ray crystal structure determinations (I, II), and in solution by H-1-, C-13-, F-19- and P-31-NMR spectroscopies. The crystal structure of complex [mu-(Bzim)Ph2PAg(NO3)](n) (n = 2, 4) (I) (triclinic, space group (no. 2), a = 15.118(5), b = 17.755(3), c = 14.123(4) Angstrom, alpha = 90.23(2), beta = 111.67(2), gamma = 85.92(2)degrees, Z = 2) shows two conformers A and B in the unit cell. The conformer A consists of a tetranuclear species formed by two [mu-(Bzim)Ph2PAg](2)(2+) moieties, related by a center of symmetry, bonded together by two bridging nitrate anions. The nitrate anions are coordinated to the sliver atoms in an unusual fashion. The conformer B is a dinuclear species where the silver atoms present in the eight-membered ring complete their tetracoordination with two chelate nitrate anions. The crystal structure of complex {[mu-(Bzim)Ph2PAg(BF4)](2)}(infinity) (II) (monoclinic, space group P2(1)/c (no. 14), a = 11.563(3), b = 8.353(4), c = 26.188(7) Angstrom, beta = 95.88(2)degrees, Z = 2) consists of infinite chains of the dinuclear cyclic silver moieties held together by BF4- bridging anions. The low temperature experimental and simulated P-31-NMR spectra of complexes I-III show complex apparent doublets of multiplets due to the resonance of the spin systems of the three isotopomers of the silver atoms present in the cyclic units. The interionic solution structure of complex II was investigated by F-19{H-1}-HOESY NMR spectroscopy. In methylene chloride solution the BF4- anion is not more coordinated to the silver(I) atoms as in the solid state, and it is localized in between the phenyl and benzyl groups of the ligand. (C) 2000 Elsevier Science S.A. All rights reserved.
2000
262
File in questo prodotto:
File Dimensione Formato  
Inorg+Chem+2013.pdf

solo gestori di archivio

Descrizione: Inorg Chem
Tipologia: Versione Editoriale
Licenza: NON PUBBLICO - Accesso privato/ristretto
Dimensione 5.01 MB
Formato Adobe PDF
5.01 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11581/466034
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 30
  • ???jsp.display-item.citation.isi??? 28
social impact