Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.

Issue 41, 2017
Previous Article Next Article

Amidine functionalized phosphines: tuneable ligands for transition metals

Author affiliations


Attachment of racemic 1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphatricyclo[,7]decane (α,β-CgP) to (1R,5S)-1,8,8-trimethyl-2,4-diazabicyclo[3.2.1]oct-2-ene gave a diastereomeric mixture of a novel amidine–phosphine ligand, α,β-CgPAm. The phosphination was completely selective for the 4-position of the bicyclic amidine and there was no subsequent 1,2-migration of the α,β-CgP group. Methylation of the non-phosphinated nitrogen gave the amidinium salt [α,β-CgPAmMe]BF4 as a diastereomeric mixture. The donating ability of α,β-CgPAm and [α,β-CgPAmMe]+ has been assessed through the synthesis and characterization of appropriate Rh(I), Au(I) and Pt(II) complexes. As expected α,β-CgPAm is a better net donor than the cationic derivative as shown by the magnitude of the νCO stretches in the IR spectra of the [Rh(L)(CO)(acac)]0/+ complexes and through determination of the relative energies of the HOMO and LUMO orbitals for both ligands by DFT. Attempts to resolve [Au(α,β-CgPAmMe)Cl]BF4, [Pt(α,β-CgPAmMe)Cl3], [Rh(α,β-CgPAmMe)(acac)(CO)]BF4 and [Rh(α,β-CgPAmH)(acac)(CO)]BF4 by fractional crystallization were unsuccessful as diastereomeric mixtures were obtained in every case; the structures of the last three complexes have been determined by single-crystal X-ray techniques and compared with related literature complexes.

Graphical abstract: Amidine functionalized phosphines: tuneable ligands for transition metals

Back to tab navigation

Supplementary files

Article information

08 Sep 2017
29 Sep 2017
First published
02 Oct 2017

Dalton Trans., 2017,46, 14234-14243
Article type

Amidine functionalized phosphines: tuneable ligands for transition metals

L. C. Wilkins, R. L. Melen, J. A. Platts and P. D. Newman, Dalton Trans., 2017, 46, 14234
DOI: 10.1039/C7DT03343E

Social activity

Search articles by author