Preparation and characterization of mixed-ligand cobalt(iii) complexes containing (3-aminopropyl)dimethylphosphine (pdmp). Conformation of the six-membered pdmp chelate ring
- 13 November 2006
- journal article
- Published by Royal Society of Chemistry (RSC) in Dalton Transactions
- No. 3,p. 308-319
- https://doi.org/10.1039/b612025c
Abstract
Several new cobalt(III) complexes containing (3-aminopropyl)dimethylphosphine (pdmp) have been prepared, and their molecular structures have been determined. A dichloro complex of trans(Cl,Cl)-cis(P,P)-[CoCl2(pdmp)2]PF6 (1) was prepared from trans-[CoCl2(py)4]Cl·6H2O and pdmp. X-Ray crystallography confirmed the (C2)-chair2 conformation of two six-membered pdmp chelate rings in 1, while the analogous 1,3-bis(dimethylphosphino)propane (dmpp) complex trans-[CoCl2(dmpp)2]ClO4 (3) exhibited the (D2d)-twist2 conformation. Substitution reactions of 1 for ethane-1,2-diamine (en), pentane-2,4-dionate (acac), and N,N-dimethyldithiocarbamate (dtc) gave the mixed-ligand tris(chelate)-type complexes of [Co(en)2(pdmp)]Cl2(PF6) (5), [Co(acac)(pdmp)2](PF6)2 (7), and [Co(dtc)3–n(pdmp)n](PF6)n [n = 1 (9) or 2 (10)], respectively. The conformer of the complex cation in 5 was assigned as lel·ob·chair by X-ray analysis. In the case of the acac complex 7, both trans(P,N) (7a) and trans(N,N) (7b) isomers were isolated, and the complex cations were characterized as syn-chair2 and anti-chair2 conformers, respectively, with respect to the six-membered pdmp chelate rings. These conformers coincide with the most stable ones anticipated by the DFT optimum geometry calculations. In the crystal structure of trans(P,N)-[Co(dtc)(pdmp)2](BPh4)2 (10′) one of the pdmp chelate rings adopted a skew-boat (twist) conformation, which reduced the intramolecular steric ring–ring interaction effectively. The DFT optimized geometries for several isomers and/or conformers of [CoCl2(pdmp)2]+ were compared.Keywords
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