Self-assembly of heteroleptic dinuclear silver(i) complexes bridged by bis(diphenylphosphino)ethyne. Issue 3 (20th December 2017)

• Record Type: Journal Article
• Authors: Keller, Sarah; Camenzind, Timothy N.; Abraham, Johannes; Prescimone, Alessandro; Häussinger, Daniel; Constable, Edwin C.; Housecroft, Catherine E.
• Is Part Of: Dalton transactions. Volume 47:Issue 3(2017)
• Page Start: 946
• Page End: 957
• Publication Date: 2017-12-20
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt03923a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The self assembly of Ag[PF6 ], bis(diphenylphosphino)ethyne and a bpy or tpy ligand was studied in solution using 31 P– 109 Ag HSQC spectroscopy and by X-ray crystallography. Abstract : We present a study of the self-assembling behaviour in solution of Ag[PF6 ] with one equivalent of an N^N ligand (N^N = 6, 6′-dimethyl-2, 2′-bipyridine (6, 6′-Me2 bpy) or 2, 2′:6′, 2′′-terpyridine (tpy)), together with either 0.5 or one equivalent of the bridging ligand bis(diphenylphosphino)ethyne (dppa). Each product contains a dinuclear cation, with one or two dppa ligands bridging the two Ag + centres; 6, 6′-Me2 bpy and tpy, respectively, act as chelating ligands. The compounds have been analysed in solution using NMR spectroscopic methods ( 1 H, 1 H{ 31 P}, COSY, NOESY, 13 C, HMQC and HMBC), including room and low temperature measurements. 31 P{ 1 H} NMR spectra recorded at different temperatures allow a deeper insight into the dynamic equilibrium processes. In addition, solution 31 P– 109 Ag HSQC spectroscopic measurements were performed and show, inter alia, the ratio of the splitting in the F1 dimension and the 1 J 31 P– 109 Ag coupling constant in the fully coupled HSQC. Single crystal X-ray diffraction yielded two pseudo-polymorphic structures for the doubly-bridged [Ag2 (dppa)2 (tpy)2 ][PF6 ]2 and one for the singly-bridged [Ag2 (dppa)(6, 6′-Me2 bpy)2 ][PF6 ]2 .