Rollover Cyclometalation with 2‑(2′-Pyridyl)quinoline
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https://figshare.com/articles/dataset/Rollover_Cyclometalation_with_2_2_Pyridyl_quinoline/2400964
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资源简介：
Rollover
cyclometalation of 2-(2′-pyridyl)quinoline, L, allowed the
synthesis of the family of complexes [Pt(L-H)(X)(L′)] and [Pt(L*)(X)(L′)][BF4] (X = Me, Cl; L′ = neutral ligand), the former being
the first examples of Pt(II) rollover complexes derived from the ligand
L. The ligand L* is a C,N cyclometalated, N-protonated isomer of L,
and can also be described as an abnormal-remote pyridylene. The corresponding
[Pt(L-H)(Me)(L′)]/[Pt(L*)(Me)(L′)]+ complexes
constitute an uncommon Brønsted–Lowry acid–base
conjugated couple. The species obtained were investigated in depth
through NMR and UV–vis spectroscopy, cyclic voltammetry, and
density functional theory (DFT) methods to correlate different chemico-physical
properties with the nature of the cyclometalated ligand (e.g., L vs
bipy or L* vs L) and of the neutral ligand (DMSO, CO, PPh3). The crystal structures of [Pt(L-H)(Me)(PPh3)], [Pt(L-H)(Me)(CO)]
and [Pt(L*)(Me)(CO)][BF4] were determined by X-ray powder
diffraction methods, the latter being the first structure of a Pt(II)-based,
protonated, rollover complex to be unraveled. The isomerization of
[Pt(L*)(Me)(PPh3)]+ in solution proceeds through
a retro-rollover process to give the corresponding adduct [Pt(L)(Me)(PPh3)]+, where L acts as a classical N,N chelating
ligand. Notably, the retro-rollover reaction is the first process,
among the plethora of Pt–C bond protonolysis reactions reported
in the literature, where a Pt–C(heteroaryl) bond is cleaved
rather than a Pt–C(alkyl) one.
创建时间：
2013-07-01
