Abstract
We have examined coordination of PR3 = triphenylphosphine, triethylphosphine, triisopropyl phosphite, trimethyl phosphite, and 1,3,5-triaza-7-phosphaadamantane (PTA) to the fragment RuII(bda) to better understand how different phosphine and phosphite ligands influence the electronic and structural properties of the RuII complexes. PTA and P(OMe)3 afforded complexes with three phosphorus ligands bound to Ru, with the bda being tridentate (κ3-N,N,O) in complexes 4 and 5; for the other three phosphorus ligands, even in the presence of >2 equiv, only RuII(κ4-bda)(PR3)2 species 1–3 were seen. Both experimental and computational methods were used to study the complexes. Steric effects are the main factor determining whether bis- or tris(PR3) complexes are formed. Cyclic voltammetry studies of the complexes revealed an increase in RuIII/II potential upon having another phosphorus ligand in the equatorial position. Computational studies predict that the additional phosphine ligand in the equatorial plane of 4 engages in significant orbital mixing with the ruthenium center that results in lower energy bonding as compared to the axial phosphine ligands. This work provides the first evaluation of phosphorus ligand steric and electronic effects on the RuII(bda) fragment.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: 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.