Steric modulation of coordination number and reactivity in the synthesis of lanthanoid(III) formamidinates

Reactions of a range of the readily prepared and sterically tunable N,N'-bis(aryl)formamidines with lanthanoid metals and bis(pentafluorophenyl)mercury (Hg(C6F5)2) in THF have given an extensive series of tris(formamidinato)lanthanoid(III) complexes, Ln(Form)3(thf)n], namely La(o-TolForm)3(thf)2], Er(o-TolForm)3(thf)], La(XylForm)3(thf)], Sm(XylForm)3], Ln(MesForm)3] (Ln=La, Nd, Sm and Yb), Ln(EtForm)3] (Ln=La, Nd, Sm, Ho and Yb), and Ln(o-PhPhForm)3] (Ln=La, Nd, Sm and Er). For an explanation of the N,N'-bis(aryl)formamidinate abbreviations used see Scheme 1.] Analogous attempts to prepare Yb(o-TolForm)3] by this method invariably yielded {Yb(o-TolForm)2(mu-OH)(thf)}2], but Yb(o-TolForm)3] was isolated from a metathesis synthesis. X-ray crystal structures show exclusively N,N'-chelation of the Form ligands and a gradation in coordination number with Ln3+ size and with Form ligand bulk. The largest ligands, MesForm, EtForm and o-PhPhForm give solely homoleptic complexes, the first two being six-coordinate, the last having an eta1-pi-Ar--Ln interaction. Reaction of lanthanoid elements and Hg(C6F5)2 with the still bulkier DippFormH in THF resulted in C--F activation and formation of Ln(DippForm)2F(thf)] (Ln=La, Ce, Nd, Sm and Tm) complexes, and o-HC6F4O(CH2)4DippForm in which the formamidine is functionalised by a ring-opened THF that has trapped tetrafluorobenzyne. Analogous reactions between Ln metals, Hg(o-HC6F4)2 and DippFormH yielded Ln(DippForm)2F(thf)] (Ln=La, Sm and Nd) and 3,4,5-F3C6H2O(CH2)4DippForm. X-ray crystal structures of the heteroleptic fluorides show six-coordinate monomers with two chelating DippForm ligands and cisoid fluoride and THF ligands in a trigonal prismatic array. The organometallic species Ln(DippForm)2(Ctriple chemical bond]CPh)(thf)] (Ln=Nd or Sm) are obtained from reaction of Nd metal, bis(phenylethynyl)mercury (Hg(Ctriple chemical bond]CPh)2) and DippFormH, and the oxidation of Sm(DippForm)2(thf)2] with Hg(Ctriple chemical bond]CPh)2, respectively. The monomeric, six-coordinate, cisoid Ln(DippForm)2(Ctriple chemical bond]CPh)(thf)] complexes have trigonal prismatic geometries and rare (for Ln) terminal Ctriple chemical bond]CPh groups with contrasting Ln--Ctriple chemical bond]C angles (Ln=Nd, 170.9(4) degrees; Ln=Sm, 142.9(7) degrees). Their formation lends support to the view that Ln(DippForm)2F(thf)] complexes arise from oxidative formation and C--F activation of Ln(DippForm)2(C6F5)] intermediates.