Issue 5, 1994

Influences of the substituents at the iminic carbon atoms (hydrogen versus methyl) upon the properties of ferrocenylimines and their cyclopalladated derivatives

Abstract

Ferrocenylimines of general formula [Fe(η5-C5H5)(η5-C5H4CR[double bond, length as m-dash]NR′)](R = Me, R′= Ph 1a, C6H4Me-2 1b, C6H4Me-4 1c, CH2Ph 1d, CH2C6H4Me-2 1e, CH2C6H4Cl-2 1f, CH2CH2Ph 1g or 1-C10H71h; R = H, R′= Ph 1i, C6H4Me-2 1j, C6H4Me-4 1k, CH2C6H4Me-2 1l, CH2C6H4Cl-2 1m or 1-C10H71n) have been prepared and characterized. Addition of these ligands to methanolic solutions of Na2[PdCl4], and sodium acetate trihydrate in a 1 : 1 molar ratio, results in the formation of the di-µ-chloro bridged cyclopalladated complex [{[graphic omitted]R′)](µ-Cl)}2]2a2n. Reaction of compounds 2a2n with triphenylphosphine in benzene yields more soluble monocyclopalladated derivatives [[graphic omitted]R′)}Cl(PPh3)]3a3n. Proton, 13C and 31P NMR spectroscopic studies on these complexes reveal that cyclopalladation occurs on the ferrocenyl moiety, thus producing five-membered metallacycles containing the C[double bond, length as m-dash]N bond (endo-type structures). The crystal structures of compounds 1a, 1i and 3g have been determined. Complex 1a is triclinic, space group P[1 with combining macron] with a= 10.152(3), b= 12.169(3), c= 12.239(3)Å, α= 90.45(2), β= 100.56(2) and γ= 102.72(2)°. Compound 1i is monoclinic, space group Cc, with a= 5.876(3), b= 37.298(9), c= 12.640(4)Å and β= 103.26(4)°. The complex [[graphic omitted]CH2CH2Ph)}Cl(PPh3)]·CH2Cl23g is monoclinic, space group P21/n with a= 20.343(2), b= 9.133(1), c= 19.714(2)Å and β= 97.17(1)°, and its crystal structure confirms the formation of a five-membered palladocycle fused with the ferrocenyl moiety. The influence of the substituents R (H or Me) and R′ upon the spectroscopic and structural properties of the free ligands and the cyclopalladated complexes is also discussed.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1994, 735-745

Influences of the substituents at the iminic carbon atoms (hydrogen versus methyl) upon the properties of ferrocenylimines and their cyclopalladated derivatives

R. Bosque, C. López, J. Sales, X. Solans and M. Font-Bardía, J. Chem. Soc., Dalton Trans., 1994, 735 DOI: 10.1039/DT9940000735

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