In this section
@article{Cooper:2022:10.1021/acs.inorgchem.2c00693,
author = {Cooper, SM and White, AJP and Eykyn, TR and Ma, MT and Miller, PW and Long, NJ},
doi = {10.1021/acs.inorgchem.2c00693},
journal = {Inorganic Chemistry: including bioinorganic chemistry},
pages = {8000--8014},
title = {N-centered tripodal phosphine Re(V) and Tc(V) oxo complexes: revisiting a [3+2] mixed-ligand approach},
url = {http://dx.doi.org/10.1021/acs.inorgchem.2c00693},
volume = {61},
year = {2022}
}
TY - JOUR
AB - N-Triphos derivatives (NP3R, R = alkyl, aryl) and asymmetric variants (NP2RXR′, R′ = alkyl, aryl, X = OH, NR2, NRR′) are an underexplored class of tuneable, tripodal ligands in relation to the coordination chemistry of Re and Tc for biomedical applications. Mixed-ligand approaches are a flexible synthetic route to obtain Tc complexes of differing core structures and physicochemical properties. Reaction of the NP3Ph ligand with the Re(V) oxo precursor [ReOCl3(PPh3)2] generated the bidentate complex [ReOCl3(κ2-NP2PhOHAr)], which possesses an unusual AA’BB’XX’ spin system with a characteristic second-order NMR lineshape that is sensitive to the bi- or tridentate nature of the coordinating diphosphine unit. The use of the asymmetric NP2PhOHAr ligand resulted in the formation of both bidentate and tridentate products depending on the presence of base. The tridentate Re(V) complex [ReOCl2(κ3-NP2PhOAr)] has provided the basis of a new reactive “metal-fragment” for further functionalization in [3 + 2] mixed-ligand complexes. The synthesis of [3 + 2] complexes with catechol-based π-donors could also be achieved under one-pot, single-step conditions from Re(V) oxo precursors. Analogous complexes can also be synthesized from suitable 99Tc(V) precursors, and these complexes have been shown to exhibit highly similar structural properties through spectroscopic and chromatographic analysis. However, a tendency for the {MVO}3+ core to undergo hydrolysis to the {MVO2}+ core has been observed both in the case of M = Re and markedly for M = 99Tc complexes. It is likely that controlling this pathway will be critical to the generation of further stable Tc(V) derivatives.
AU - Cooper,SM
AU - White,AJP
AU - Eykyn,TR
AU - Ma,MT
AU - Miller,PW
AU - Long,NJ
DO - 10.1021/acs.inorgchem.2c00693
EP - 8014
PY - 2022///
SN - 0020-1669
SP - 8000
TI - N-centered tripodal phosphine Re(V) and Tc(V) oxo complexes: revisiting a [3+2] mixed-ligand approach
T2 - Inorganic Chemistry: including bioinorganic chemistry
UR - http://dx.doi.org/10.1021/acs.inorgchem.2c00693
UR - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000805762800033&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=a2bf6146997ec60c407a63945d4e92bb
UR - https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c00693
UR - http://hdl.handle.net/10044/1/112415
VL - 61
ER -
Professor Nick Long
Email: n.long@imperial.ac.uk
Telephone: +44 (0)20 7594 5781
501J
Molecular Sciences Research Hub
White City Campus
