Synthesis and structural characterization of [eta superscript 3]-allyl([alpha]-diimine)nickel(II) complexes bearing trimethylsilyl groups
Journal Article
·
· Journal of Organometallic Chemistry
- Dupont
A set of isomeric para- and meta-trimethylsilylphenyl ortho-substituted N,N-phenyl {alpha}-diimine ligands [(Ar-N C(Me)-(Me)C N-Ar) Ar=2,6-di(4-trimethylsilylphenyl)phenyl (16); Ar=2,6-di(3-trimethylsilylphenyl)phenyl (17)] have been synthesized through a two-step procedure. The palladium-catalyzed cross-coupling reaction between 2,6-dibromophenylamine (7) and 4-trimethylsilylphenylboronic acid (8), 3-trimethylsilylphenylboronic acid (9) was used to prepare 4,4-bis(trimethylsilyl)-[1,1;3,1]terphenyl-2-ylamine (10) and 3,3-bis(trimethylsilyl)-[1,1;3,1]terphenyl-2-ylamine (11). The di-1-adamantylphosphine oxide Ad{sub 2}P(O)H (13) and di-tert-butyl-trimethylsilylanylmethylphosphine tert-Bu{sub 2}P-CH{sub 2}-SiMe{sub 3} (14) were used for the first time as ligands for the Suzuki coupling. The condensation of 2,2,3,3-tetramethoxybutane (15) with anilines 10 and 11 afforded {alpha}-diimines 16 and 17. The reaction of {pi}-allylnickel chloride dimer (18), {alpha}-diimines (16), (17) and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAF) (19) or silver hexafluoroantimonate (20) led to two sets of isomeric complexes [{eta}{sup 3}-allyl(Ar-N C(Me)-(Me)C N-Ar)Ni]{sup +} X{sup -}, [Ar=2,6-di(4-trimethylsilylphenyl)phenyl, X=BAF (3), X=SbF6 (4); Ar=2,6-di(3-trimethylsilylphenyl)phenyl, X=BAF (5), X=SbF6 (6)]. The steric repulsion of closely positioned trimethylsilyl groups in 4 caused the distortion of the nickel square planar coordination by 17.6{sup o} according to X-ray analysis.
- Research Organization:
- Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- OSTI ID:
- 1034935
- Journal Information:
- Journal of Organometallic Chemistry, Journal Name: Journal of Organometallic Chemistry Journal Issue: 6 Vol. 689; ISSN 0022-368X; ISSN JORCAI
- Country of Publication:
- United States
- Language:
- ENGLISH
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