TY - JOUR
T1 - Plasticity of the Nickel(II) coordination environment in complexes with hemilabile phosphino thioether ligands
AU - MacHan, Charles W.
AU - Spokoyny, Alexander M.
AU - Jones, Matthew R.
AU - Sarjeant, Amy A.
AU - Stern, Charlotte L.
AU - Mirkin, Chad A.
PY - 2011/3/9
Y1 - 2011/3/9
N2 - A series of homoligated Ni(II) complexes formed from two phosphino thioether (P,S) chelating ligands has been synthesized and characterized. Interestingly, this included octahedral Ni(II) complexes which, unlike previously characterized d8 Rh(I), Pt(II), and Pd(II) analogues, exhibit in situ exchange processes centered around chloride ligand dissociation. This was verified and studied through the controlled abstraction from and introduction of chloride ions to this system, which showed that these processes proceed through complexes with square pyramidal, tetrahedral, and square planar geometries. These complexes were studied with a variety of characterization methods, including single-crystal X-ray diffraction studies, solution 31P{1H} NMR spectroscopy, UV-vis spectroscopy, and DFT calculations. A general set of synthetic procedures that involve the use of coordinating and noncoordinating counteranions, as well as different hemilabile ligands, to mediate geometry transformations are presented.
AB - A series of homoligated Ni(II) complexes formed from two phosphino thioether (P,S) chelating ligands has been synthesized and characterized. Interestingly, this included octahedral Ni(II) complexes which, unlike previously characterized d8 Rh(I), Pt(II), and Pd(II) analogues, exhibit in situ exchange processes centered around chloride ligand dissociation. This was verified and studied through the controlled abstraction from and introduction of chloride ions to this system, which showed that these processes proceed through complexes with square pyramidal, tetrahedral, and square planar geometries. These complexes were studied with a variety of characterization methods, including single-crystal X-ray diffraction studies, solution 31P{1H} NMR spectroscopy, UV-vis spectroscopy, and DFT calculations. A general set of synthetic procedures that involve the use of coordinating and noncoordinating counteranions, as well as different hemilabile ligands, to mediate geometry transformations are presented.
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U2 - 10.1021/ja109624m
DO - 10.1021/ja109624m
M3 - Article
C2 - 21319748
AN - SCOPUS:79952253525
VL - 133
SP - 3023
EP - 3033
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 9
ER -