Synthesis And Structure Of Paddlewheel Dibismuthane(?),Distibine(?) And Lanthanide Complexes Bearing 1,2,4-Diazaphospholide Ligands

The paddlewheel complex has better chemical stability,which has a good application prospect in the field of organic cactalyic reaction as potential catalyst.However,the main group metallic paddlewheel complexes were difficultly sythnsized because of their properties.In addition,lanthanide complexes containing alkali metals are popular in the family of lanthanide complexes,which are of great interest in homogeneous catalysis,as there is a synergic effect between lanthanide ions and alkali metals.The preparation of novel charge-separated heterobimetallic,or alkali metalate lanthanide complexes has attracted our attention because such complexes are expected to be potential effective catalysts in varied organic reaction,and precursors for synthesis the low-valent rare earth complexes.In this paper,a series of paddlewheel dibismuthane?II?,distibine?II?and lanthanide complexes with 1,2,4-diazaphospholide ligands have been synthesized and characterized by X-ray single crystal diffraction analysis,IR and NMR.The main work was summarized as follows.?1?1,2,4-diazaphospholide dibismuthanes [{?1,?1-3,5-R2dp}2?Bi-Bi?{?1,?1-3,5-R2dp}2]?R = t Bu?4?,i Pr?5?,Ph?6??were prepared by Bi Cl₃ and [3,5-R2dp]-?R = t Bu,i Pr,Ph?.The Bi-Bi single bond in 4?2.796 ??was even shorter than the Bi=Bi double bonds?2.82 ??in dibismuthene Tbt-Bi=Bi-Tbt?Tbt = 2,4,6-tris?bis?trimethylsilyl?methyl?phenyl?.?2?1,2,4-diazaphospholide distibines [{?1,?1-3,5-R2dp}2?Sb-Sb?{ ?1,?1-3,5-R2dp}2]?R =t Bu?9?,i Pr?10?,Cy?11??were prepared by Sb Cl₃ and [3,5-R2dp]-?R = t Bu,i Pr,Cy?.The Sb-Sb single bond in 9?2.669 ??was even close to the Sb=Sb double bonds?2.655??in distibene 2,6-Mes2H3C6Sb=Sb C6H3-2,6-Mes2?Mes = C6H2-2,4,6-Me3?.?3?[??2?N,N?-3,5-t Bu2dp?2Pr?THF?2Cl]2?15?was prepared by Pr Cl₃?THF?2 and[?3,5-t Bu2dp?K] in a ratio of 1 : 2.A few novel heteroleptic complexes [??2?N,N?-3,5-t Bu2dp?3M?THF?2]?M = La^Nd?was prepared by MCl₃·m THF?M = La,R = t Bu,m =1.36;M = Ce,R = t Bu,m = 1.46;M = Pr,R = t Bu,m = 2.0;M = Nd,R = t Bu,m = 1.99;M = Pr,R = Ph,m = 2.0?and [?3,5-t Bu2dp?K] in a ratio of 1 : 3.[??2?N,N?-3,5-Ph2dp?3Pr?THF?3]?20?was prepared by MCl₃·m THF M = Pr,R = Ph,m = 2.0 and[?3,5-Ph2dp?K]·0.67 THF in a ratio of 1 : 3.The reaction of [?3,5-t Bu2dp?K] or[?3,5-Ph2dp?K]·0.67 THF and Sm Cl₃·1.98 THF in a ratio of 1 : 4 provided charge-seperated heterobimetallic complexes {[K?THF?5]+[??2?N,N?-3,5-Ph2dp?4Sm?THF?]-}?21?or {[K?THF?6]+[??2?N,N?-3,5-t Bu2dp?4Sm]-}?22?.The polymeric alkali metalate complexes of 1,2,4-diazaphospholide Lanthanum?III??23?and Samarium?III??24?was prepared by MCl₃·m THF?M = La,m = 1.36;M = Sm,m =1.98?and K[3,5-Ph2dp] in a ratio 1 : 5.The magnetic susceptibility studies of 18 and 19 showed that the magnetic moments are close to or lower than the theoretical values for the free ion in the trivalent oxidation states?Pr3+and Nd3+?.