Square-planar ruthenium(II) complexes: control of spin state by pincer ligand functionalization.
Chemistry
; 21(2): 579-89, 2015 Jan 07.
Article
in En
| MEDLINE
| ID: mdl-25359612
ABSTRACT
Functionalization of the PNP pincer ligand backbone allows for a comparison of the dialkyl amido, vinyl alkyl amido, and divinyl amido ruthenium(II) pincer complex series [RuCl{N(CH2 CH2 PtBu2 )2 }], [RuCl{N(CHCHPtBu2 )(CH2 CH2 PtBu2 )}], and [RuCl{N(CHCHPtBu2 )2 }], in which the ruthenium(II) ions are in the extremely rare square-planar coordination geometry. Whereas the dialkylamido complex adopts an electronic singlet (S=0) ground state and energetically low-lying triplet (S=1) state, the vinyl alkyl amido and the divinyl amido complexes exhibit unusual triplet (S=1) ground states as confirmed by experimental and computational examination. However, essentially non-magnetic ground states arise for the two intermediate-spin complexes owing to unusually large zero-field splitting (D>+200â
cm(-1) ). The change in ground state electronic configuration is attributed to tailored pincer ligand-to-metal π-donation within the PNP ligand series.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Ruthenium
/
Coordination Complexes
Language:
En
Journal:
Chemistry
Journal subject:
QUIMICA
Year:
2015
Document type:
Article