New silyl-nickel complexes prepared by η6-arene substitution in (η6-toluene)bis(trihalosilyl)nickel. Preparation of L3Ni(SiX3)2 and L2Ni(SiX3)2 (X = Cl, F; L = phosphine, phosphites, and pyridines. X-Ray structure of cis-(collidine)2Ni(SiCl3)2
| Autor: | Lewis J. Radonovich, Kenneth J. Klabunde, Seok-Burm Choe, Thomas A. Ballintine, Joerg J. Schneider |
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| Rok vydání: | 1989 |
| Předmět: |
Steric effects
Chemistry Stereochemistry Ligand Organic Chemistry Trimethylphosphine chemistry.chemical_element Biochemistry Inorganic Chemistry chemistry.chemical_compound Trigonal bipyramidal molecular geometry Nickel Crystallography Pyridine Materials Chemistry Physical and Theoretical Chemistry Triethylphosphite Phosphine |
| Zdroj: | Journal of Organometallic Chemistry. 376:419-439 |
| ISSN: | 0022-328X |
| Popis: | Facile displacement of the arene ligand in (η 6 -toluene)Ni(SiX 3 ) 2 (X = F, Cl) has produced L 2 Ni(SiX 3 ) 2 and L 3 Ni(SiX 3 ) 2 complexes, where L = trimethylphosphine, triethylphosphine, trimethylphosphite, triethylphosphite, trifluorophosphine, pyridine, lutidine, or collidine. Steric factors appear to determine whether disubstituted (square planar) or trisubstituted (trigonal bipyramidal) systems are formed. In the case of the methyl-pyridine analogs the cis - and trans -L 2 Ni(SiCl 3 ) 2 complexes can be differentiated by their NMR. These investigations have led to a wide range of new Ni-Si complexes, some of their chemical properties have been investigated, and an improved synthesis of (η 6 -toluene)Ni(SiF 3 ) 2 is reported. An X-ray structure determination of Ni(SiCl 3 ) 2 ((CH 3 ) 3 C 5 H 2 N) 2 reveals that a distorted square planar geometry exists in the solid state with equivalent ligands in a cis -configuration. The complex crystallizes in space group P 2 1 / c with lattice constants of a 8.964(5), b 15.0591(9), c 18.273(1) A, and β 86.689(2)°. The steric bulk of the collidine ligand is accommodated by a ∼28° rotation of the NiN 2 plane relative to the NiSi 2 plane which is closer to square planar (0°) than tetrahedral (90°). An analysis of bond parameters indicates that some π-backbonding to the SiCl 3 groups exists which helps to stabilize the complex. |
| Databáze: | OpenAIRE |
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