Issue 17, 2017

Mono- and polynuclear Ag(i) complexes of N-functionalized bis(diphenylphosphino)amine DPPA-type ligands: synthesis, solid-state structures and reactivity

Abstract

The reactivity of the N-functionalized DPPA-type ligands (Ph2P)2N(p-Z)C6H4 [Z = H (1a), SMe (1b), OMe (1c)] with AgBF4 was investigated and revealed an unexpected influence of the para substituent Z of the N-aryl ligand. In acetone, the mononuclear bis-chelated [Ag{(1a–1c)-P,P}2]BF4 (2a·BF42c·BF4) and dinuclear bridged [Ag22-(1a–1c)-P,P}2](BF4)2 [3a·(BF4)23c·(BF4)2] complexes were obtained with a 1 : 2 and 1 : 1 AgBF4/ligand molar ratio, respectively. While the molecular structures of 2a·BF4 and 2b·BF4 determined in the solid-state by X-ray diffraction revealed their mononuclear nature and the absence of cation/anion interaction, complexes 3b·(BF4)2 and 3c·(BF4)2 form 2D coordination polymers through intermolecular Ag–S or Ag–O interactions, respectively, involving the N-function of the respective DPPA-type ligand, and display direct interactions between one BF4 anion and both Ag(I) cations. Surprisingly, the equimolar reaction between ligands 1a–1c and AgBF4 in CH2Cl2 led to different proportions of the dinuclear complexes 3a·(BF4)23c·(BF4)2 and clusters [Ag33-Cl)22-(1b–1c)-P,P}3]BF4 (4b·BF44c·BF4), depending on the nature of the para substituent Z of the N-aryl ligand. The trinuclear complexes resulted from C–Cl bond activation of the chlorinated solvent and were characterized by NMR spectroscopy and X-ray diffraction, and could be selectively produced by addition of 2/3 equiv. of [NMe4]Cl to the corresponding dinuclear complexes or by a one-pot procedure involving the correct amount of each reagent. A series of experiments and kinetic NMR investigations were performed to gain further insight into the formation of the trinuclear Ag3Cl2 core clusters.

Graphical abstract: Mono- and polynuclear Ag(i) complexes of N-functionalized bis(diphenylphosphino)amine DPPA-type ligands: synthesis, solid-state structures and reactivity

Supplementary files

Article information

Article type
Paper
Submitted
16 Dec. 2016
Accepted
09 Marts 2017
First published
22 Marts 2017

Dalton Trans., 2017,46, 5571-5586

Mono- and polynuclear Ag(I) complexes of N-functionalized bis(diphenylphosphino)amine DPPA-type ligands: synthesis, solid-state structures and reactivity

A. Ghisolfi, C. Fliedel, P. de Frémont and P. Braunstein, Dalton Trans., 2017, 46, 5571 DOI: 10.1039/C6DT04755F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements