title: Novel Cyclopentadienyl-Free Organolanthanides: The First Examples of Five-Membered Amidolanthanide Heterocycles.
abstract: Reactions of LnCl(3) (Ln = Nd, Gd, Yb) and [{Me(2)SiN(R)Li}(2)] (R = t-Bu, Ph) give the chloride-bridged dimers [{{(t-Bu)NSiMe(2)SiMe(2)N(t-Bu)}Ln(&mgr;-Cl)(THF)}(2)] (1, Ln = Nd; 2, Ln = Gd; 3, Ln = Yb) and [{{(Ph)NSiMe(2)SiMe(2)N(Ph)}Ln(&mgr;-Cl)(THF)(2)}(2)] (4, Ln = Nd; 5, Ln = Gd; 6, Ln = Yb) in good yields. Compounds 2 and 5 were structurally characterized by X-ray crystallography: 2, triclinic, P&onemacr;, a = 10.321(2) Å, b = 11.116(2) Å, c = 13.434(3) Å, alpha = 107.57(3) degrees, beta = 111.31(3) degrees, gamma = 90.67(3) degrees, V = 1356.1(5) Å(3), Z = 1, R = 0.0233; 5, monoclinic, P2(1)/n, a = 13.913(13) Å, b = 12.914(9) Å, c = 16.434(14) Å, beta = 105.64(3) degrees, V = 2843(4) Å(3), Z = 2, R = 0.0281. The chloro functions in 1-6 remain reactive, demonstrated by the isolation of the trifluoroacetate derivatives of 1 and 2. Treatment of 1 or 2 with 2 equiv of NaOCOCF(3) gives [{{(t-Bu)NSiMe(2)SiMe(2)N(t-Bu)}Ln(&mgr;-OCOCF(3))(THF)}(2)] (7, Ln = Nd; 8, Ln = Gd). The structure of 8 was determined by a single-crystal X-ray diffraction analysis. Crystal data for 8: triclinic, P&onemacr;, a = 11.045(2) Å, b = 16.120(3) Å, c = 16.949(3) Å, alpha = 66.17(3) degrees, beta = 85.51(3) degrees, gamma = 78.27(3) degrees, V = 2702.9(9) Å(3), Z = 2, R = 0.0311. The structure of 8 shows the trifluoroacetate group adopting a bridging bidentate mode of coordination.
authors.affiliation: Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Syed A. A.
authors.initials: SA
authors.lastname: Shah
authors.forename: Hendrik
authors.initials: H
authors.lastname: Dorn
authors.forename: Herbert W.
authors.initials: HW
authors.lastname: Roesky
authors.forename: Paolo
authors.initials: P
authors.lastname: Lubini
authors.forename: Hans-Georg
authors.initials: HG
authors.lastname: Schmidt