Monomeric Bis(pentamethylcyclopentadienyl)titanium(III) Complexes with Halide, Borohydride, Amide, Alkoxide, and Carboxylate Ligands: X-ray Structure of Bis(pentamethylcyclopentadienyl)titanium(III) Chloride

Johannes W. Pattiasina, Hero J. Heeres, Fré van Bolhuis, Auke Meetsma, Jan H. Teuben, Anthony L. Spek

OnderzoeksoutputAcademicpeer review

114 Citaten (Scopus)

Samenvatting

The synthesis and characterization of monomeric Cp*2TiX complexes (X = Cl, Br, I, BH4, OCMe3, O2CH) are reported. These 15-electron d1 systems have one unpaired electron and form perfect Curie paramagnetic systems. They are NMR and ESR active. 1H NMR spectra show broad lines (width 600-5000 Hz) for the Cp* hydrogens between 14.0 and 18.4 ppm. Observation of the protons of the non-Cp* ligands is possible if they are positioned at least β with respect to the metal. The ESR spectra are singlets (g = 1.939-1.978), with for some complexes the expected Ti isotope hyperfine splitting. Hyperfine splittings due to interaction with hydrogen or other nuclei of the ligands are not observed. The structure of Cp*2TiCl (1) was determined by X-ray diffraction. 1 crystallizes in the monoclinic space group P21/n, with a = 9.339 (2) Å, b = 13.632 (1) Å, c = 15.140 (3) Å, β = 99.55 (1)°, and Z = 4. The structure was refined to R = 0.045 and Rw = 0.050 for 290 parameters and 2909 observed reflections (with F > 3σ(F)). The molecule exhibits an approximate twofold noncrystallographic axis along the Ti-Cl bond. The chlorine ligand is coordinated in the equatorial plane of a bent-sandwich permethyltitanocene fragment (Ti-Cl = 2.363 (1) Å). The Cp* rings coordinate in a true η5 way to the metal. Methyl-methyl contacts between the staggered Cp* ligands cause a deviation of one of the methyl groups out of the plane of the ring and away from the metal of 0.40 (1) Å.
Originele taal-2English
Pagina's (van-tot)1004-1010
Aantal pagina's7
TijdschriftOrganometallics
Volume6
Nummer van het tijdschrift5
DOI's
StatusPublished - mei-1987

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