Metallorganische Titankomplexe mit ungepaarten Elektronen: Synthese und Struktur von [{(η⁵‐Cp)₂TiF₂}₃Ti und [{(η⁵‐Cp')₂TiF₂}₃Al]

Abstract

Verzerrt oktaedrisch und propellerartig sind die zentralen Metallatome in Kristallen von 1 und 2 umgeben. Diese Komplexe sind die ersten metallorganischen Fluorotitan(III)‐Komplexe und auch die ersten paramagnetischen Titankomplexe mit mehr als zwei Ti‐Atomen. R = Cp. [(Cp2TiF2)3Ti] 1 [(Cp2TiF2)3Al] 2

Difference in Reactivity of Cyclopentadienyltitanium Fluorides and Chlorides Using AlR3 (R = Me, Et): Syntheses and Structures of Ti(III)−F(Cl)−Al Compounds (η5-C5Me5)2Ti2(μ-Cl)6Al2Me4, (η5-C5Me5)2Ti2(μ-F)8Al4Me8, and [(η5-C5H4Me)2Ti(μ-F)2AlEt2]2

“…It is interesting to note that the C atoms of the Al−methyl groups are not directly involved in the disorder; only the Al atoms which are connected to them change and the methyl H atoms are disordered. In compound 4 the average Ti−F bond distance is 2.06 Å (average Al−F 1.76 Å) and is comparable to those determined in compound 6 (Ti−F 2.11 Å and Al−F 1.74 Å, average) and [Cp 2 Ti(μ-F) 2 ] 3 Al (Ti−F 2.09 Å, Al−F 1.81 Å, average), whereas the average F−Al−F (95.5°) angle is smaller than that in 6 (103°). It is interesting to note that there are two types of F−Ti−F angles in 4 (average 80.1° and 128.9°).…”

Formation of [Cp2Ti(μ2-F)2AlEt2]2 and [Cp(C5H4)Ti(μ2-H)AlEt2]2 in the Reaction of Cp2TiF2 with AlEt3. Structure of [Cp2Ti(μ2-F)2AlEt2]2

“…The Ti−Ti distance (5.841 Å) indicates no metal−metal bond to be formed. The Ti−F (2.10 Å) and Al−F (1.73 Å) average bond distances are comparable to those in compound (Cp 2 TiF 2 ) 3 Al ( 4 ) (Ti−F 2.09 Å, Al−F 1.81 Å, average, respectively) . However, all F−Ti−F (78.53°), F−Al−F (100.18°), and Al−F−Ti (160.13°, 169.08°) angles in 2 are larger than those found in complex 4 (F−Ti−F (68.29°), F−Al−F (80.91°), Al−F−Ti (105.40°)).…”

Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block Metals

“…Formation of metal−fluorine bonds, Al−F and Ga−F bonds in 77 − 79 , appears to be a strong thermodynamic driving force for these reactions. In related zinc and manganese reductions no corresponding Zn−F or Mn−F bond formation is observed. , It seems likely in the light of this work that the unidentified precursor of 70 is also a dimetallic complex of formulation (Cp‘ 2 TiF) 3 AlF 3 .…”