TY - JOUR
T1 - SYNTHESIS AND REACTIVITY OF TERVALENT PARAMAGNETIC TITANIUM COMPOUNDS (ETA-5-C5ME5)2TIR - MOLECULAR-STRUCTURE OF (ETA-5-C5ME5)2TICH2CME3
AU - LUINSTRA, GA
AU - TENCATE, LC
AU - HEERES, HJ
AU - PATTIASINA, JW
AU - MEETSMA, A
AU - TEUBEN, JH
PY - 1991/9
Y1 - 1991/9
N2 - Paramagnetic, tervalent titanium compounds Cp*2TiR with R = Me (2), Et (3), n-Pr (4), CH2CMe3 (5), CH2Ph (6), eta-3-C3H5 (7), eta-3-C4H7 (8), CH = CH2 (9), C = CMe (10), Ph (11) have been prepared by salt metathesis from Cp*2TiCl (1). 1 The H-1 NMR spectra show characteristic broad resonances (width at half-maximum between 0.88 and 5.5 kHz) in the range-delta 14.5-20.9 ppm, which are due to the H-1 nuclei of the Cp* ligands. Only part of the H-1 resonances of the carbyl ligand R are observed. H-2 NMR spectra of Cp*2TiR with deuterated ligands R allow assignment of all H-2 nuclei in R. These are observed between delta -79 and 125 ppm. Solution EPR spectra show broad singlet signals in the range g = 1.941-1.992, without hyperfine interaction with H-1 nuclei of the ligands or titanium isotope splitting. The crystal structure of 5 was determined by a single-crystal X-ray diffraction study. The compound crystallizes in the monoclinic space group P2(1)/n with four molecules in the unit cell. The cell dimensions are a = 10.221 (2) angstrom, b = 15.609 (3) angstrom, c = 14.107 (3) angstrom, and beta = 94.21 (2)-degrees. The refinements converged at R(F) = 0.059 for 2801 observed reflections and 359 parameters. Thermolysis of the compounds leads to quantitative formation of RH and a (pentamethylcyclopentadienyl)(fulvene)titanium compound, Cp*FvTi (Fv = eta-6-C5Me4CH2). The 15-electron compounds Cp*2TiR do not form stable adducts Cp*2TiR.L, although intermediate adduct formation is indicated in reactions with substrates such as CO and isonitriles. With CO a complicated reaction occurs in which disproportionation to Ti(II) and Ti(IV), acyl formation, and nucleophilic attack on the Cp* ligand with ring expansion takes place. With isonitriles RN = C insertion in the Ti-R bond leads to formation of eta-2-iminoacyls. Carbon dioxide reacts to give carboxylates Cp*2Ti(eta-2-O2CR). For alkyls Cp*2TiR, where R bears a beta-hydrogen, the dominant process is beta-H transfer to an incoming substrate molecule and extrusion of the olefin R(-H). This has been observed for 3 and 4 with carbon dioxide, olefins, and but-2-yne.
AB - Paramagnetic, tervalent titanium compounds Cp*2TiR with R = Me (2), Et (3), n-Pr (4), CH2CMe3 (5), CH2Ph (6), eta-3-C3H5 (7), eta-3-C4H7 (8), CH = CH2 (9), C = CMe (10), Ph (11) have been prepared by salt metathesis from Cp*2TiCl (1). 1 The H-1 NMR spectra show characteristic broad resonances (width at half-maximum between 0.88 and 5.5 kHz) in the range-delta 14.5-20.9 ppm, which are due to the H-1 nuclei of the Cp* ligands. Only part of the H-1 resonances of the carbyl ligand R are observed. H-2 NMR spectra of Cp*2TiR with deuterated ligands R allow assignment of all H-2 nuclei in R. These are observed between delta -79 and 125 ppm. Solution EPR spectra show broad singlet signals in the range g = 1.941-1.992, without hyperfine interaction with H-1 nuclei of the ligands or titanium isotope splitting. The crystal structure of 5 was determined by a single-crystal X-ray diffraction study. The compound crystallizes in the monoclinic space group P2(1)/n with four molecules in the unit cell. The cell dimensions are a = 10.221 (2) angstrom, b = 15.609 (3) angstrom, c = 14.107 (3) angstrom, and beta = 94.21 (2)-degrees. The refinements converged at R(F) = 0.059 for 2801 observed reflections and 359 parameters. Thermolysis of the compounds leads to quantitative formation of RH and a (pentamethylcyclopentadienyl)(fulvene)titanium compound, Cp*FvTi (Fv = eta-6-C5Me4CH2). The 15-electron compounds Cp*2TiR do not form stable adducts Cp*2TiR.L, although intermediate adduct formation is indicated in reactions with substrates such as CO and isonitriles. With CO a complicated reaction occurs in which disproportionation to Ti(II) and Ti(IV), acyl formation, and nucleophilic attack on the Cp* ligand with ring expansion takes place. With isonitriles RN = C insertion in the Ti-R bond leads to formation of eta-2-iminoacyls. Carbon dioxide reacts to give carboxylates Cp*2Ti(eta-2-O2CR). For alkyls Cp*2TiR, where R bears a beta-hydrogen, the dominant process is beta-H transfer to an incoming substrate molecule and extrusion of the olefin R(-H). This has been observed for 3 and 4 with carbon dioxide, olefins, and but-2-yne.
KW - RAY CRYSTAL-STRUCTURE
KW - CARBON-MONOXIDE
KW - ETHYLENE POLYMERIZATION
KW - CHAIN PROPAGATION
KW - NMR-SPECTROSCOPY
KW - ALKYL COMPLEXES
KW - METAL-COMPLEXES
KW - DERIVATIVES
KW - BOND
KW - ACTIVATION
M3 - Article
SN - 0276-7333
VL - 10
SP - 3227
EP - 3237
JO - Organometallics
JF - Organometallics
IS - 9
ER -