Hydrostannylation of Olefins by a Hydridostannylene Tungsten Complex
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https://figshare.com/articles/dataset/Hydrostannylation_of_Olefins_by_a_Hydridostannylene_Tungsten_Complex/21578947
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资源简介：
Reaction of the aryltin(II) hydride {AriPr6Sn(μ-H)}2 (AriPr6 =
−C6H3-2,6-(C6H2-2,4,6-iPr3)2)
with two equivalents of the tungsten carbonyl THF complex, [W(CO)5(THF)], afforded the divalent tin hydride transition metal
complex, W(CO)5{Sn(AriPr6)H},
(1). Complex 1 reacted rapidly with ethylene,
or propylene under ambient conditions to yield the corresponding hydrostannylated
organometallic species, W(CO)5{Sn(AriPr6)(Et)} (2), or W(CO)5{Sn(AriPr6)(nPr)} (3), via olefin insertion into the Sn–H bond. Treatment
of 1 with the Lewis base dbu (dbu = 1,8-diazabicycloundec-7-ene)
afforded the Lewis acid–base complex, W(CO)5{Sn(AriPr6)(dbu)H} (4), indicating
that the Lewis acidity of the tin atom is preserved in 4. The complexes were characterized by X-ray crystallography, and
by UV–visible, FT-IR, and multinuclear NMR spectroscopies.
DFT calculations suggest hydrostannylation of ethylene with 1 proceeds via coordination of ethylene to the tin atom, then
insertion into the Sn–H bond. Further computational study on
the reactivity of 1 toward Ph3SiH indicated
that the rate-determining step involves the metathesis reaction of
a Sn–C/Si–H bond with a very high energy barrier of
71.3 kcal/mol. The calculated proton abstraction product of 1 with dbu, [W(CO)5{Sn(AriPr6)}]+[H(dbu)]−, is 18.2 kcal/mol
less stable than the observed coordination product 4.
创建时间：
2022-12-12
