Homoleptische Amide von Zink, Cadmium und Quecksilber

Abstract

ZnCl2, CdCl2 und HgCl2 reagieren mit den Lithiumsalzen (1 a–5 a) der sterisch anspruchsvollen sekundären Amine HN(SiMe3)Ph (1), HN(SiMe3)C6H3Me2‐2,6 (2), HN(SiMe3)C6H3iPr2‐2,6 (3), HN(SiMe3)C6H3tBu2‐2,5 (4) und HN(SiMe2NMe2)C6H3iPr2‐2,6 (5) unter Bildung der entsprechenden homoleptischen Metallamide Zn[N(SiMe2R′)R]2 (1 b–5 b), Cd[N(SiMe2R′)R]2 (1 c, 5 c) und Hg[N(SiMe2R′)R]2 (1 d–5 d). Mit Ausnahme des dimeren {Zn[N(SiMe3)Ph]2}2 (1 b) sind alle Verbindungen monomer. Die Charakterisierung der Verbindungen erfolgte durch Elementaranalysen, Molekulargewichtsbestimmungen, NMR‐ und Massenspektren. Die darüberhinaus durch Einkristall‐Röntgenstrukturanalysen charakterisierten Zink‐ (1 b–5 b) und Quecksilberverbindungen (1 d–3 d und 5 d) zeigen mit Ausnahme von 1 b und 5 b eine lineare N–M–N Anordnung.

Syntheses and structures of highly hindered N-functionalised alkyl and amido group 12 complexes MR2 (M=Zn, Cd, and Hg), [MRCl]2 (M=Zn and Hg)

“…Atom deviations ( A) from the C 5 N plane dM 0.26(1), 0.11(1) 0.13 (3), 0.04 (1) 0.27 (4), 0.03(4) 0.542 (7) 0.55(1) dM 0 )0.18 (1), )0.21 (1) )0.07 (3), )0.12 (3) )0.06 (4), )0.09 (4) 0.196 (7) 0.10(1) dSi (11) 1.48(1), 1.51 (2) 1.49(4), 1.56 (5) 1.58(4), 1.51 (5) 1.311 (9) 1.38(1) dSi (21) 1.81(1), 1.74 (1) 1.72(4), 1.72 (3) 1.69(4), 1.61 (4) 1.404 (8) 1.49(1) dSi (12) )1.66 (1), )1.66 (2) )1.69(4), )1.65 (4) )1.61(4), )1.72 (5) )1.740 (8) )1.71(1) dSi (22) )1.30 (1), )1.37 (1) )1.45(4), )1.46 (4) )1.52 (5), )1.59 (5) )1.734 (7) )1.79 (1) Plane 1/plane 2 interplanar dihedral angles (°) 85.9 (3), 89.5 (3) 88.5 (8), 89.5 (9) 89.4 (9), 89.5 (10) 48.9(2) 47.6 (3) The two values for the isomorphous Mg(HR) 2 , 3 and 4 are for the two molecules of the asymmetric unit. [M(HR) 2 ], suggestive of increased strain.…”

“…The synthesis and chemistry of group 12 alkyl and amido complexes has received considerable attention in recent years [7][8][9][10][11][12]. Herein, we report syntheses and structural studies of an array of functionalised pyridine complexes of zinc, cadmium and mercury based on a range of ligands with varying substitutions.…”

Chlorido{N-[(diethylamino)dimethylsilyl]anilido-κN}(N,N,N′,N′-tetramethylethane-1,2-diamine-κ2N,N′)cobalt(II)

“…For the catalytic applications of related Nsilylated analido-group 4 metal compounds towards olefin polymerization, see: Gibson et al (1998); Hill & Hitchcock (2002); Yuan et al (2010). For related organometallic compounds with analogous analido ligands, see: Schumann et al (2000); Chen (2008Chen ( , 2009.…”

“…It was presumed that the empty d-orbitals on silicon would interact with the lone-pair electrons on the porbital of nitrogen center through d-pπ interaction throughout the N-Si-N motif. Analogous compounds with different metals including Zn (Schumann et al, 2000), Zr (Chen, 2009) and Fe (Chen, 2008) have been synthesized. A group of zirconium amides with the similar ligand were reported showing good performance in ethylene polymerization (Yuan et al, 2010).…”

True Blue Inorganic Optoelectronic Devices

“…[147,148] The research groups of Power et al [149] and Raston et al [150] synthesized and characterized Zn[N(SiMePh 2 ) 2 ] 2 and Zn[N(8-quinolyl)(SiMe 3 )] 2 , respectively. Recently, other dialkylamines [151,152] were used to produce novel amides, e.g., diisopropylamine, [103,142] diisobutylamine, [103,142] N,N-dimethylaminoethylmethylamine, [103] and bis-N,N-diethylaminoethylamine. [103] …”