Late-stage ligand functionalization <i>via</i> the Staudinger reaction using phosphine-appended 2,2′-bipyridine
作者:Deeb Taher、Jessica R. Wilson、Grayson Ritch、Matthias Zeller、Nathaniel K. Szymczak
DOI:10.1039/d1cc01407b
日期:——
platform for late-stage ligand modifications was evaluated using tetrahedral (Ph2P)2bpyFeCl2. We employed a post-metalation Staudinger reaction to install a series of functionalized arenes, including those containing Brønsted and Lewis acidic groups. This reaction sequence represents a versatile strategy to both tune the ligand donor properties as well as directly incorporate appended functionality
Rearrangement of the Ag4 cores of the luminescent silver(I) bis(diphenylphosphanyl)bipyridine (P2-bpy) complexes shown upon ligation of the Ag centers (see picture) leads to quenching of their emissions. Quenching occurs with O2, CO, NO, and with coordinating solvents such as MeCN and Me2SO. The reversible quenching of the emission of the halide-free complex [Ag4(P2-bpy)2]4+ in solution suggests potential applications as a sensor.
Synthesis and Characterization of Pd(0) and Pt(0) Metallocryptands Encapsulating Tl<sup>+</sup> Ion
作者:Vincent J. Catalano、Byron L. Bennett、Renante L. Yson、Bruce C. Noll
DOI:10.1021/ja001672s
日期:2000.10.1
Pt(0)/Pd(0) metallocryptates encapsulating TI(I) have been constructed utilizing mixed phosphine-imine ligands 2,9-bis(diphenylphosphino)-1,10-phenathroline, P(2)phen, and 6,6'-bis(diphenylphosphino)-2,2'-bipyridine, P(2)bpy. The red compounds [M2Tl(P(2)phen)(NO3) (M = Pt, 1; M = Pd, 3) and [M2Tl(P(2)bpy)(3)](NO3) (M = Pt, 2; M = Pd, 4) have been isolated as air-stable crystalline solids. Complexes 1-4 exhibit single signals in their Tl-205 NMR spectra that are well deshielded compared to the TiNO3(aq) reference signal. Additionally, Pt-195 NMR spectra of complexes 1 and 2 exhibit a doublet of quartets pattern resulting from large one-bond couplings to both P-31 and Tl-205. Characterization of 1-4 by single-crystal X-ray diffraction studies confirms the metallocryptand structure consisting of three phosphine-imine ligands in a D-3-symmetric cage with the TI(I) ion in its center and the zero-valent Pt or Pd atoms on each end. Each Pd or Pt atom is coordinated to three phosphorus centers, forming approximately trigonal geometry. The Tl(I) ion is positioned away from the imine nitrogen atoms of the phosphine ligands by similar to3.5 Angstrom. Further, the outer capping metals are distorted toward the central TI(I) ion, indicating a strong interaction. The Pt-Tl and Pd-TI separations are at similar to2.8 Angstrom each, further manifesting the strength of the metallophilic attraction in these assemblies.
Bahsoun, Ali A.; Ziessel, Raymond, Nouveau Journal de Chimie, 1985, vol. 9, p. 225 - 228