%0 Journal Article %1 Kaim.2011c %A Kaim, Wolfgang. %D 2011 %J Inorganic Chemistry %K active complex ligand metal noninnocent redox review transition %N 20 %P 9752--9765 %R 10.1021/ic2003832 %T Manifestations of Noninnocent Ligand Behavior %V 50 %X A review. The potential of redox-active ligands to behave \dqnoninnocently\dq in transition-metal coordination compds. is reflected with respect to various aspects and situations. These include the question of establishing \dqcorrect\dq oxidn. states, the identification and characterization of differently charged radical ligands, the listing of structural and other consequences of ligand redox reactions, and the distinction between barrierless delocalized \dqresonance\dq cases Mn/Ln $łeftrightarrow$ Mn+1Ln-1 vs. sepd. valence tautomer equil. situations Mn/Ln .dblharw. Mn+1Ln-1. Further ambivalence arises for dinuclear systems with radical bridge Mn(m-L·)Mn vs. mixed-valent alternatives Mn+1(m-L-)Mn, for noninnocent ligand-bridged coordination compds. of higher nuclearity such as (m3-L)M3, (m4-L)M4, (m-L)4M4, or coordination polymers. Conversely, the presence of more than one noninnocently behaving ligand at a single transition-metal site in situations such as Ln-M-Ln-1 or L·-M-L· may give rise to corresponding ligand-to-ligand interaction phenomena (charge transfer, electron hopping, and spin-spin coupling) and to redox-induced electron transfer with counterintuitive oxidn.-state changes. The relations of noninnocent ligand behavior with excited-state descriptions and perspectives regarding material properties and single-electron or multielectron reactivity are also illustrated briefly. on SciFinder(R)

@article{Kaim.2011c, abstract = {A review. The potential of redox-active ligands to behave {\dq}noninnocently{\dq} in transition-metal coordination compds. is reflected with respect to various aspects and situations. These include the question of establishing {\dq}correct{\dq} oxidn. states, the identification and characterization of differently charged radical ligands, the listing of structural and other consequences of ligand redox reactions, and the distinction between barrierless delocalized {\dq}resonance{\dq} cases Mn/Ln $\leftrightarrow$ Mn+1Ln-1 vs. sepd. valence tautomer equil. situations Mn/Ln .dblharw. Mn+1Ln-1. Further ambivalence arises for dinuclear systems with radical bridge Mn(\textgreek{m}-L·)Mn vs. mixed-valent alternatives Mn+1(\textgreek{m}-L-)Mn, for noninnocent ligand-bridged coordination compds. of higher nuclearity such as (\textgreek{m}3-L)M3, (\textgreek{m}4-L)M4, (\textgreek{m}-L)4M4, or coordination polymers. Conversely, the presence of more than one noninnocently behaving ligand at a single transition-metal site in situations such as Ln-M-Ln-1 or L·-M-L· may give rise to corresponding ligand-to-ligand interaction phenomena (charge transfer, electron hopping, and spin-spin coupling) and to redox-induced electron transfer with counterintuitive oxidn.-state changes. The relations of noninnocent ligand behavior with excited-state descriptions and perspectives regarding material properties and single-electron or multielectron reactivity are also illustrated briefly. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/24668d47f74fa0bcb2683796160a1a4fb/huebleriac}, doi = {10.1021/ic2003832}, interhash = {720a5dab7ae3df1047e88bd87632d6eb}, intrahash = {4668d47f74fa0bcb2683796160a1a4fb}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {active complex ligand metal noninnocent redox review transition}, number = 20, pages = {9752--9765}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Manifestations of Noninnocent Ligand Behavior}, volume = 50, year = 2011 }