Abstract
The primary and secondary coordination spheres can have large regulatory effects on the properties of metal complexes. To examine their influences on the properties of monomeric Fe complexes, the tripodal ligand containing phosphinic amido groups, N,N',N''-[nitrilotris(ethane-2,1-diyl)]tris(P,P-diphenylphosphinic amido) ([poat]3-), was used to prepare [FeII/IIIpoat]-/0 complexes. The FeII complex was four-coordinate with 4 N-atom donors comprising the primary coordination sphere. The FeIII complex was six-coordinate with two additional ligands coming from coordination of O-atom donors on two of the phosphinic amido groups in [poat]3-. In the crystalline phase, each complex was part of a cluster containing potassium ions in which KO[double bond, length as m-dash]P interactions served to connect two metal complexes. The [FeII/IIIpoat]-/0 complexes bound an NH3 molecule to form trigonal bipyramidal structures that also formed three intramolecular hydrogen bonds between the ammine ligand and the O[double bond, length as m-dash]P units of [poat]3-. The relatively negative one-electron redox potential of -1.21 V vs. [FeIII/IICp2]+/0 is attributed to the phosphinic amido group of the [poat]3- ligand. Attempts to form the FeIII-amido complex via deprotonation were not conclusive but isolation of [FeIIIpoat(NHtol)]- using the p-toluidine anion was successful, allowing for the full characterization of this complex.
Accepted Version
Published Version
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
