Low-Valent Pentafulvene Titanium Dinitrogen Complex as a Precursor for Cationic Titanium Complexes

Treatment of titanium dinitrogen complex [Cp*(η6-C5H4=C10H14)Ti]2(μ-N2) (1) with ferrocenium borate, [Cp2Fe][BPh4], in THF results in oxidation of the titanium center, affording the titanium(IV) pentafulvene compound [Cp*(η6-C5H4=C10H14)Ti(THF)][BPh4]. Treatment of 1 with anilinium reagent [PhNMe2H][BPh4] results in the formation of cationic titanocene(III) complexes. In THF, the titanocene cation is stabilized by two THF solvent molecules, whereas the tetraphenylborate anion is bound to the metal center when the reaction is performed in toluene as a solvent. Treatment of 1 with B(C6F5)3 affords zwitterionic [Cp*{η5-C5H3(C11H14)(B{C6F5}3)}Ti(THF)]. Results show the versatility of pentafulvene complex 1 in the preparation of cationic titanium complexes.

Tetrabenzo[a,c,g,i]fluorenyltitanium(III) and -(IV) complexes: Syntheses, reactions, and catalytic application

Reacting tetrabenzo[a,c,g,i]fluorenyllithium {TbfLi(THF)(4) (1)} with TiCl(3)(THF)(3) (2) leads to the formation of the eta(5)-tetrabenzo[a,c,g,i]fluorenyltitanium(III) derivative TbfTiCl(2)(THF) (3), which can be conveyed to the titanium(IV)complex TbfTiCl(3) (4) by oxidative chlorination with CCl(4). Subsequent reaction with various lithium phenoxides gives a series of titanium complexes of the type TbtTiCl(2)(OAr) (Ar = 4-(t)BUC(6)H(4) (5), 2,6-Me(2)C(6)H(3) (6), 2,4,6-Me(3)C(6)H(2) (7), 2,6-(i)PrC(6)H(3) (8), 2,6-Ph(2)C(6)H(3) (9)). Furthermore, 3 was reacted with radicals or radical-generating peroxides to form the complexes TbfTiCl(2)TEMPO (10) and TbfTiCl(2)O(t)Bu (11). All compounds were characterized by IR, MS, and NMR measurements and X-ray crystallography. Finally, compounds 6, 8, 9, and 10 were subjected to ethylene polymerization experiments using d-MAO. The activities increase in the following order [kG(PE)mol(Ti)(-1) h(-1) bar(-1)]: 6 (320) <8 (320) <10 (760) <9 (1000)

CCDC 670168: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 670169: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 670165: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 670170: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 670172: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 670173: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 670171: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

CCDC 670167: Experimental Crystal Structure Determination

Related Article: K.Schroder, D.Haase, W.Saak, R.Beckhaus, W.P.Kretschmer, A.Lutzen|2008|Organometallics|27|1859|doi:10.1021/om7012293,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.