Steinborn, Dirk; Becke, Frank; Boese, Roland:

Synthesis and Properties of (Aminomethyl)nickel Complexes. [{Li(OEt2)}2Ni(CH2NC5H10)4]: The First Structurally Characterized Homoleptic Aminomethyl Complex of a Transition Metal.

In: Inorganic chemistry (Inorg.Chem.), Jg. 34 (1995) ; Nr. 10, S. 2625-2628
ISSN: 0020-1669
Zeitschriftenaufsatz / Fach: Chemie
Bu3SnCH2NR2 (R2N = Me2N, C5H10N, Ph2N) react with BuLi to give R2NCH2Li.xTHF (1a, R2N = Me2N, x = 0; 1b, R2N = C5H10N, x = 0; 1c, R2N = Ph2N, x = 1). 1A and 1b react with Ni halide phosphine adducts to give very air-sensitive homoleptic aminomethyl complexes of Ni [{Li(OEt2)}2Ni(CH2NR2)4] (2a, R2N = Me2N; 2b, R2N = C5H10N), which were characterized anal. and spectroscopically by NMR. 2 Is diamagnetic, is thermally very stable [Tdec: 90-115 Deg (2a); 95-110 Deg (2b)], and reacts with H2O and alcs. to give R2NMe. The crystal structure of 2b (space group P21/c; R = 0.0656) exhibits a mol. Ci symmetry. There is a planar NiC4 unit [d(Ni-C) 2.023(4), 2.032(4) .ANG.] and a nearly trigonal planar coordination of Li at R2N and Et2O as well as Li contacts to Ni [d(Li-Ni) 2.592(2) .ANG.] and to C atoms R2NCH2Ni of the piperidinomethyl ligands [d(Li-C) 2.166(7), 2.312(8) .ANG.].