1033091-65-4Relevant academic research and scientific papers
A phosphine-mediated through-space exchange coupling pathway for unpaired electrons in a heterobimetallic lanthanide-transition metal complex
Raturi, Ritu,Lefebvre, Julie,Leznoff, Daniel B.,McGarvey, Bruce R.,Johnson, Samuel A.
, p. 721 - 730 (2008)
The reaction of P(CH2OH)3 with methyl anthranilate NH2C6H4-2CO2Me produced the ligand precursor P(CH2NHC6H4-2-CO2Me) 3 (1). The reaction of 1 with [Y(N(SiMe3)) 2]3] produced hexadentate yttrium complex [Y(P(CH 2NC6H4-2-CO2Me)3}] (2), in which the metal centre is coordinated by three amido donors and the three carbonyl oxygen atoms of the ester groups. The 31P(1H) NMR spectrum features 1JY,P= 15 Hz, and DFT calculations demonstrate that through-space interaction between the minor lobe of the phosphine lone pair and the yttrium centre allows a large Fermi contactcontribution to this spin coupling constant. The EPR spectrum of the analogous paramagnetic Gd complex [Gd[P(CH2NC6H 4-2-CO2Me)3)] (3) can be modelled by using a B20 crystal field parameter of ±0.19 cm-1. Heterodinuclear complexes were prepared by the reactions of 1 and 3 with [5,10,15,20tetrakis(4-methoxyphenyl)porphinato]cobalt(II), by binding of the phosphinelone pair to the d7 cobalt centre. The solid-state EPR spectrum of the heterodinuclear yttrium complex 4 exhibits large superhyperfine coupling to the phosphorus nucleus, indicative of an S=1/2 complex in which the unpaired electron resides in the cobalt dz2 orbital directed at the phosphine donor. The magnetic susceptibility of the heterodinuclear Gd-Co complex S demonstrates that through-space antiferromagnetic coupling occurs between unpaired electrons on the gadolinium and cobalt centres.
