Heteroleptic Heavier Alkaline Earth Metal Amide Complexes
Stabilized by a Superbulky β‑Diketiminate Ligand
Version 2 2019-05-31, 18:42
Version 1 2019-05-28, 19:35
Posted on 2019-05-31 - 18:42
Heteroleptic alkaline earth metal
(Ae = Ca, Sr, Ba) amide complexes
with the superbulky β-diketiminate ligand DIPePBDI
(CH[C(Me)N-DIPeP]2, DIPeP = 2,6-di-iso-pentylphenyl) have been prepared by direct deprotonation of DIPePBDI-H with either AeN′′2 or AeN′′2·(THF)2 (N′′ = N(SiMe3)2). Despite long reaction times of 5–14 days,
this convenient one-step synthetic method has the major advantage
that metal-pure products are obtained in generally quantitative yields.
All (DIPePBDI)AeN′′ and (DIPePBDI)AeN′′·THF complexes are monomeric and
stabilized by agostic metal···Me3Si and
metal···iso-pentyl interactions. They
are highly soluble in toluene and indefinitely stable toward ligand
scrambling, even after 2 weeks at 140 °C. The same series with
the smaller DIPPBDI ligand (CH[C(Me)N-DIPP]2, DIPP = 2,6-di-iso-propylphenyl) could, except
for Ca, also be prepared by direct ligand deprotonation. The (DIPPBDI)CaN′′ and (DIPPBDI)CaN′′·THF
complexes are stable toward ligand exchange up to 110 °C. Whereas
THF-free (DIPPBDI)SrN′′ and (DIPPBDI)BaN′′ decompose at 50 and 20 °C, respectively,
their THF adducts were found to be stable up to 60 °C. This is,
however, strongly dependent on complex purity. Slight hydrolysis or
contamination with KN′′ accelerates ligand scrambling.
Therefore, partial hydrolysis and salt metathesis routes that involve
KN′′ should be avoided when synthesizing heteroleptic
complexes of the heavier Ae metals.
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Gentner, Thomas
Xaver; Rösch, Bastian; Thum, Katharina; Langer, Jens; Ballmann, Gerd; Pahl, Jürgen; et al. (2019). Heteroleptic Heavier Alkaline Earth Metal Amide Complexes
Stabilized by a Superbulky β‑Diketiminate Ligand. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.9b00211
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AUTHORS (9)
TG
Thomas
Xaver Gentner
BR
Bastian Rösch
KT
Katharina Thum
JL
Jens Langer
GB
Gerd Ballmann
JP
Jürgen Pahl
WD
Wolfgang A. Donaubauer
FH
Frank Hampel
SH
Sjoerd Harder
KEYWORDS
ligand deprotonationsuperbulky β- diketiminate ligand DIPeP BDIligand exchangepentyl interactionsAe metalsisosalt metathesis routesCH2 weeksmetal-pure productsKNDIPP BDI ligandearth metalTHF adductsSlight hydrolysisamide complexesreaction timesDIPeP BDI-HHeteroleptic Heavier Alkaline Earth Metal Amide Complexes Stabilizedsynthesizing heteroleptic complexes