Honaolcpiic 2.2 '-btpyrid,vl comptc,~c~ t~l laulh:midcs (Ln), I..lt~bp.,. i4. ~vcrc prepared by the reactions of iodides Lnl2(TH t=) 2 {Ln = Sin. ELI, Im, or Yb), t.nl ~(lHFh ~[.n := La. (7c. Pr, Nd, Gd. or Tb). or bis(irimcthylsilyl.bamidc,, L~q N(SiMc~)2I 3 {I..n = D3,. t lo, Er, or I.u) with bipyridyllitllium it~ tclrahydrofura~l (IHF) or 1.2-dinlciho\ycthanc ill ihc presence of frcc 2,2 "-bipyridmc. The IR and ESR spectral data. the magnclic sust:cpiibditic',, and Ihe resells of X-ray diffraction analysis illdic;ltc ihat the conlplcxes of ;ill clclncilis ol the tanlhanidc series, t.,xccpt 10r the" ctlropitlli/complc\, cllnlalll Ell <~ C/lliOlls glP, d atliOillC bpv tigand>. ACCOl'dillg tO tile X-fdV dil/rclctioll dcliil, the c,,>ordhlalitUl l~olyhcdra ahotll the Sin :.llld [:.tl :lloms :ire tribes. Key words: rare-torah clenaci~ts, 2.2 "-bip.,,ridinc. comptc'xcs, ,,;ifticltlfc. magliclic: 0ropcrtics.Recently, wc i3ave initiated a scries of studies aimed at the SVllthesis o( complexes of rare-earth cletllellts with the chelating 2,2"-bipyridyl (bpy) ligartd This ligar~d po.,,-sesscs both a-donor (four-electron N-donor) ae, d =-acceptor properties. Successive reduction of the ligand allows one to prcpare its mollO-and dianionic lorms. Bigyridyl complexes of many mctals are known. In the ease of d-block elements, the ligaud acts to a greater cxtcllt as at1 n-donor and the LUMO of the ligand ietllaiils unoccupied, whereas clectropositi,,e metals can lorm comple~,es both with nl(.mo-and dJallions, Pre~i-otlsly, we have prepared various complexes of rare-earth clcments with bpy'-radical anions. Among them, three types can be distinguished: (a) the mixed bpy-DAD complex of samarium ISm~:~(DAD-' )(DAD-)(bpy~ ~DAD = BuINCHCHNBtH): I (b) the aniollic complcxes J Li(TH F)4J+[Ln(bp.v)nl-iLn = Sin, Tb, Tin, Yb, or De. n = 3 or 4), which were synthesizect by the reactions of iodides with Li(bpy) in TI-IF: z and (c) the mixed iodinc-bpy complexes of ytterbium(n), vi:.. Ybl(bpy)(DME)~, 3 and lanthanum(Ill), viz,, Lal2(bpy)~DME) 2 aud Lal_,(-bpy)~l'DME), 4 which were lormed in the reactions of the corresponding iodinenaphthalene complexes [YbI(DME)_,I2(bI-Ct0H~i) or ll.alz(fHt:)zJ_~(.u-Cj0H ,) with one or two equivalents of bpy. Recently, 5 we have reported the syHthcsis and X-ray diffraction study of the first complex of latlthanidc with the bipyridyl diarti