1H, 13C and 31P studies of cyclopentadienylruthenium complexes with cyclooctatetraene or cyclooctadiene ligands. X-ray structure of [(η5-C5H5)Ru(η4-C8H8)(P(OCH3)3)]PF6

Amy M. McNair, Thomas P. Gill, Kent R. Mann

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Abstract

The X-ray crystal structure of [(η5-C5H5)Ru(η4-COT)(P(OCH3)3)]PF6 (COT = cyclooctatetraene) (formula C16H22F6O3P2Ru) was determined. The compound crystallizes in the monoclinic space group no. 4 P21 (a 11.007(3), b 11.066(3), c 8.660(3) Å, β 105.56(20)°, Z = 2). The structure consists of discrete disordered PF6- anions and [(η5-C5H5)Ru(η4-COT)(P(OCH3)3)]+ cations. The cation exhibits a planar, C5H5- unit. (RuC distances of 2.221(7) Å), a P(OCH3)3 ligand (RuP distance of 2.306(2) Å) and an η4-COT ligand in the tub conformation. The η4-COT ligand is bound to the Ru atom through two different Ru bond distances 2.298(5) and 2.223(6) Å, the longer distance appropriate to the RuC bonds nearest the RuP bond. The 1H, 13C and 31P NMR spectra of [(η5-C5H5)Ru(η4-COT) (P(OCH3)3)]PF6,[(η5-C5H5)Ru(η4-COT)(CO)PF6,[(η5-C5H5)Ru(η6-COT)PF6 and [(η5-C5H5)Ru(η4-COD)(P(OCH3)3]PF6 (COD = 1,5-cyclooctadiene) were obtained. Comparison of the 1H NMR and 13C spectra of [(η5-C5H5)Ru(η4-COT)(P(OCH3)3]PF6 and [(η5-C5H5)Ru(η4-COD)(P(OCH3)3)]PF6 confirm that the COT complex retains the solid state structure in solution. Through comparison and simulation of the 1H and 1H{31P} NMR spectra of [(η5-C5H5)Ru(η4-COT)(P(OCH3)3)]PF6 all eight COT protons are found to exhibit 1H-31P coupling. The allylic coupling constants that involve hydrogens bound to a coordinated carbon have small positive values, rather than the small negative values usually found in 'pure' organic systems.

Original languageEnglish (US)
Pages (from-to)99-116
Number of pages18
JournalJournal of Organometallic Chemistry
Volume326
Issue number1
DOIs
StatePublished - May 26 1987

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