Pentamethylcyclopentadienyl Half-Sandwich Diazoalkane Complexes of Ruthenium: Preparation and Reactivity
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https://figshare.com/articles/dataset/Pentamethylcyclopentadienyl_Half_Sandwich_Diazoalkane_Complexes_of_Ruthenium_Preparation_and_Reactivity/3382411
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资源简介：
The
diazoalkane complexes [Ru(η5-C5Me5)(N2CAr1Ar2){P(OR)3}L]BPh4 (1–4) [R = Me, L = P(OMe)3 (1); R = Et, L = P(OEt)3 (2); R = Me, L = PPh3 (3); R = Et, L = PPh3 (4); Ar1 = Ar2 = Ph (a); Ar1 =
Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (c); Ar1 = Ph, Ar2 = PhC(O) (d)] and [Ru(η5-C5Me5){N2C(C12H8)}{PPh(OEt)2}(PPh3)]BPh4 (5c)
were prepared by allowing chloro-compounds RuCl(η5-C5Me5)[P(OR)3]L to react
with the diazoalkane Ar1Ar2CN2 in the presence of NaBPh4. Treatment of complexes 1–4 with H2O afforded 1,2-diazene derivatives [Ru(η5-C5Me5)(η2-NHNH){P(OR)3}L]BPh4 (6–9)
and ketone Ar1Ar2CO. A reaction path involving nucleophilic attack
by H2O on the coordinated diazoalkane is proposed and supported
by density functional theory calculations. The complexes were characterized
spectroscopically (IR and 1H, 31P, 13C, 15N NMR) and by X-ray crystal structure determination
of [Ru(η5-C5Me5)(N2CC12H8){P(OEt)3}2]BPh4 (2c) and [Ru(η5-C5Me5)(η2-NHNH){P(OEt)3}2]BPh4 (7).
创建时间：
2016-05-31
