10.1021/ja050521s.s007
Jianfang Chai
Jianfang
Chai
Vojtech Jancik
Vojtech
Jancik
Sanjay Singh
Sanjay
Singh
Hongping Zhu
Hongping
Zhu
Cheng He
Cheng
He
Herbert W. Roesky
Herbert W.
Roesky
Hans-Georg Schmidt
Hans-Georg
Schmidt
Mathias Noltemeyer
Mathias
Noltemeyer
Narayan S. Hosmane
Narayan S.
Hosmane
Synthesis of a New Class of Compounds Containing a
Ln−O−Al Arrangement and Their Reactions and Catalytic
Properties
American Chemical Society
2005
complexes 1
refluxing conditions
HC
New Class
6 exhibit
diketiminate ligand
Cp 3 Ln compounds
2 Cl
intramolecular elimination
LYbCp 2
HN
Catalytic Properties Synthesis
proton exchange process
3 SnF
Compounds Containing
2005-05-25 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Synthesis_of_a_New_Class_of_Compounds_Containing_a_Ln_O_Al_Arrangement_and_Their_Reactions_and_Catalytic_Properties/3285007
Synthesis of a new class of compounds containing a Ln−O−Al moiety has been accomplished
by the reaction of LAlOH(Me) (L = HC(CMeNAr)<sub>2</sub>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) with a series of Cp<sub>3</sub>Ln compounds.
The terminal Al−OH group shows selective reactivity, and the complexes Cp<sub>2</sub>Ln(THF)−O−AlL(Me) (Ln =
Yb, <b>1</b>; Er, <b>2</b>; Dy, <b>3</b>), Cp<sub>2</sub>Yb−O−AlL(Me) (<b>4</b>), and Cp<sub>3</sub>Ln(μ-OH)AlL(Me) (Ln = Er, <b>5</b>; Dy, <b>6</b>; Sm, <b>7</b>) were
obtained. This allows further insight into the proton exchange process, and two different mechanisms,
intermolecular and intramolecular elimination of CpH, are proposed under different conditions. Complexes
<b>1</b>−<b>4</b>, <b>6</b>, and <b>7</b> have been characterized by X-ray structural analyses which reveals a Ln−O−Al or Ln(μ-OH)Al core in these complexes. The obtuse Ln−O−Al angles fall in the range 151.9−169.8°. The reaction
of <b>1</b> or <b>4</b> with Me<sub>3</sub>SnF in toluene under refluxing conditions unexpectedly yielded the compounds [Cp<sub>2</sub>Yb(μ-OSnMe<sub>3</sub>)]<sub>2</sub> (<b>8</b>) and LAl(Me)F (<b>9</b>). Reactions of LAlOH(Me) with the mono- and dicyclopentadienyl
complexes LYbCp(Cl) (<b>10</b>) and LYbCp<sub>2</sub> (<b>11</b>) supported by the bulky <i>β</i>-diketiminate ligand were unsuccessful.
However, the reaction of LAl(OH)Me with LYbN(SiMe<sub>3</sub>)<sub>2</sub>Cl (<b>12</b>) containing a labile Yb−N bond leads to the
formation of LYbCl−O−AlL(Me) (<b>13</b>) under elimination of HN(SiMe<sub>3</sub>)<sub>2</sub>. Furthermore, complexes<b> 1</b>, <b>3</b>, <b>4</b>,
and <b>6</b> exhibit good catalytic activity for the polymerization of <i>ε</i>-caprolactone.