Dihydroperimidine-Derived PNP Pincer Complexes as Intermediates en Route to N‑Heterocyclic Carbene Pincer Complexes
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https://figshare.com/articles/dataset/Dihydroperimidine_Derived_PNP_Pincer_Complexes_as_Intermediates_en_Route_to_N_Heterocyclic_Carbene_Pincer_Complexes/2302612
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资源简介：
The reaction of N,N′-bis(dicyclohexylphosphinomethyl)dihydroperimidine
(H2C(NCH2PCy2)2C10H6-1,8, 1a) with [RuCl2(PPh3)3] in THF affords the perimidinylidene-based N-heterocyclic
carbene (per-NHC) pincer complex [RuCl2(OC4H8){C(NCH2PCy2)2C10H6}] (2) via chelate-assisted
double C–H activation. In contrast, the reactions of the tetraphenyl
analogue H2C(NCH2PPh2)2C10H6 (1b) with [RuCl2(PPh3)3] and of 1a with [RuCl(R)(CO)(PPh3)2] (R = Ph, CHCHPh) do not result in C–H
activation but rather give the asymmetric, PNP-coordinated complexes
[RuCl2(PPh3){κ3P,N,P′-CH2(NCH2PPh2)2C10H6}]
(3) and [RuCl(R)(CO){κ3P,N,P′-CH2(NCH2PCy2)2C10H6}]
(R = Ph (4), CHCHPh (5)), respectively,
in which the ruthenium migrates rapidly between nitrogen donors. This
provides insight into the mechanistic pathway by which the proligands 1 undergo per-NHC formation, as demonstrated
by the thermal conversion of 4 to [RuHCl(CO){C(NCH2PCy2)2C10H6}]
(6) and benzene.
创建时间：
2014-04-28
