Dimethylcalcium
收藏NIAID Data Ecosystem2026-03-10 收录
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https://figshare.com/articles/dataset/Dimethylcalcium/5852994
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资源简介：
The salt metathesis reaction between
homoleptic calcium bis(trimethylsilyl)amide
[Ca{N(SiMe3)2}2]2 and
“halide-free” methyllithium allowed for the isolation
of X-ray-amorphous dimethylcalcium [CaMe2]n in good yields and purities. The formation of [CaMe2]n was proven by microanalysis
and NMR/FTIR spectroscopic methods as well as a series of derivatization
reactions. Despite slowly decomposing thf, [CaMe2]n could be crystallized from chilled thf solutions
as the heptametallic adduct [(thf)10Ca7Me14]. Reaction of [CaMe2]n with CaI2 in thf led to the dimeric complex
[(thf)3Ca(Me)(I)]2, whereas in tetrahydropyran
(thp) the trinuclear complex [(thp)5Ca3(Me)5(I)] was obtained, both representing the first crystallographically
characterized heavy-Grignard compounds with methyl groups as the hydrocarbyl
ligand. While protonolysis of [CaMe2]n with the superbulky proligand HTptBu,Me in nonpolar solvents gave homoleptic (TptBu,Me)2Ca, reaction in donor solvents (thf, thp) afforded the
monomeric complexes [(TptBu,Me)Ca(Me)(thf)]
and [(TptBu,Me)Ca(Me)(thp)], which
are the first examples bearing terminal Ca–CH3 functionalities.
Grignard-type nucleophilic methyl-group transfer to hexamethylacetone
gave access to the dimeric alkoxide complexes [(thf)Ca(OCtBu2Me)2]2 and [(tBu2CO)Ca(μ2-OCtBu2Me)3Ca(OCtBu2Me)]. Finally, addition of the Lewis acid GaMe3 to [CaMe2]n led to
the corresponding tetramethylgallate compound [Ca(GaMe4)2]n.
创建时间：
2018-01-12
