2-(Arylamino)-4,6-di- tert -butylphenols containing 4-substituted phenyl groups ( R apH 2 ) react with oxobis(ethylene glycolato)osmium( vi ) in acetone to give square pyramidal bis(amidophenoxide)oxoosmium( vi ) complexes. A mono-amidophenoxide complex is observed as an intermediate in these reactions. Reactions in dichloromethane yield the diolate ( H ap) 2 Os(OCH 2 CH 2 O). Both the glycolate and oxo complex are converted to the corresponding cis -dichloride complex on treatment with chlorotrimethylsilane. The novel bis(aminophenol) ligand EganH 4 , containing an ethylene glycol dianthranilate bridge, forms the chelated bis(amidophenoxide) complex (Egan)OsO, where the two nitrogen atoms of the tetradentate ligand bind in the trans positions of the square pyramid. Structural and spectroscopic features of the complexes are described well by an osmium( vi )-amidophenoxide formulation, with the amount of π donation from ligand to metal increasing markedly as the co-ligands change from oxo to diolate to dichloride. In the oxo-bis(amidophenoxides), the symmetry of the ligand π orbitals results in only one effective π donor interaction, splitting the energy of the two osmium-oxo π* orbitals and rendering the osmium-oxo bonding appreciably anisotropic.
Highly covalent metal–ligand π bonding in chelated bis- and tris(iminoxolene) complexes of osmium and ruthenium
The bis(aminophenol) 2,2′-biphenylbis(3,5-di- tert -butyl-2-hydroxyphenylamine) (ClipH 4 ) forms trans -(Clip)Os(py) 2 upon aerobic reaction of the ligand with {( p -cymene)OsCl 2 } 2 in the presence of pyridine and triethylamine. A more oxidized species, cis -β-(Clip)Os(OCH 2 CH 2 O), is formed from reaction of the ligand with the osmium( vi ) complex OsO(OCH 2 CH 2 O) 2 , and reacts with Me 3 SiCl to give the chloro complex cis -β-(Clip)OsCl 2 . Octahedral osmium and ruthenium tris-iminoxolene complexes are formed from the chelating ligand tris(2-(3′,5′-di- tert -butyl-2′-hydroxyphenyl)amino-4-methylphenyl)amine (MeClampH 6 ) on aerobic reaction with divalent metal precursors. The complexes’ structural and electronic features are well described using a simple bonding model that emphasizes the covalency of the π bonding between the metal and iminoxolene ligands rather than attempting to dissect the parts into discrete oxidation states. Emphasizing the continuity of bonding between disparate complexes, the structural data from a variety of Os and Ru complexes show good correlations to π bond order, and the response of the intraligand bond distances to the bond order can be analyzed to illuminate the polarity of the bonding between metal and the redox-active orbital on the iminoxolenes. The osmium more »
- Award ID(s):
- 1465104
- Publication Date:
- NSF-PAR ID:
- 10331411
- Journal Name:
- Dalton Transactions
- Volume:
- 49
- Issue:
- 21
- Page Range or eLocation-ID:
- 7015 to 7027
- ISSN:
- 1477-9226
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
The tris(aminophenol) ligand tris(4-methyl-2-(3′,5′-di- tert -butyl-2′-hydroxyphenylamino)phenyl)amine, MeClampH 6 , reacts with Ti(O i Pr) 4 to give, after exposure to air, the dark purple, neutral, diamagnetic complex (MeClamp)Ti. The compound is six-coordinate, with an uncoordinated central nitrogen (Ti–N = 2.8274(12) Å), and contains titanium( iv ) and a doubly oxidized ligand, formally a bis(iminosemiquinone)-mono(amidophenoxide). The compound is unsymmetrical in the solid state, though the three ligands are equivalent on the NMR timescale in solution. Ab initio calculations indicate that the ground state is a multiconfigurational singlet, with a low-lying multiconfigurational triplet state. Variable-temperature NMR measurements are consistent with a singlet–triplet gap of 1200 ± 70 cm −1 , in good agreement with calculations. The distortion from threefold symmetry allows a low-lying, partially populated ligand-centered π nonbonding orbital to mix with largely occupied metal–ligand π bonding orbitals. The energetic accessibility of this distortion is inversely related to the strength of the metal–ligand π bonding interaction.
-
In this work, we investigated bonding features of 15 ruthenium(II) nitrile complexes of the type [Ru(tpy)(L)-(CH 3 CN)] n+ , containing the tridentate tpy ligand (tpy = 2,2′:6′,2″-terpyridine) and various bidentate ancillary ligands L; 12 compounds originally synthesized by Loftus et al. [J. Phys. Chem. C 123, 10291–10299 (2019)] and three new complexes. We utilized local vibrational force constants derived from the local mode theory as a quantitative measure of bond strength complemented with the topological analysis of the electron density and the natural bond orbital analysis. Loftus et al. suggested that nitrile dissociation occurs after light induced singlet–triplet transition of the original complexes and they used as a measure of nitrile release efficiency quantum yields for ligand exchange in water. They observed larger quantum yields for complexes with smaller singlet–triplet energy gaps. The major goal of this work was to assess how the Ru–NC and Ru–L bond strengths in these 15 compounds relate to and explain the experimental data of Loftus et al., particularly focusing on the question whether there is a direct correlation between Ru–NC bond strength and measured quantum yield. Our study provides the interesting result that the compounds with the highest quantum yields also have themore »
-
Structural analyses of the compounds di-μ-acetato-κ 4 O : O ′-bis{[2-methoxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ]manganese(II)} bis(tetraphenylborate) dichloromethane 1.45-solvate, [Mn 2 (C 23 O 2 ) 2 (C 23 H 23 N 3 O) 2 ](C 24 H 20 B)·1.45CH 2 Cl 2 or [Mn(DQMEA)(μ-OAc) 2 Mn(DQMEA)](BPh 4 ) 2 ·1.45CH 2 Cl 2 or [1] (BPh 4 ) 2 ·1.45CH 2 Cl 2 , and (acetato-κ O )[2-hydroxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ](methanol-κ O )manganese(II) tetraphenylborate methanol monosolvate, [Mn(CH 3 COO)(C 22 H 21 N 3 O)(CH 3 OH)](C 24 H 20 B)·CH 3 OH or [Mn(DQEA)(OAc)(CH 3 OH)]BPh 4 ·CH 3 OH or [2] BPh 4 ·CH 3 OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to Mn II ions. In the asymmetric unit, compound [1] (BPh 4 ) 2 ·(CH 2 Cl 2 ) 1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitrogen, the nitrogen atom of each quinoline group, and the methoxy-oxygen of the tetradentate DQMEA ligand, and two bridging-acetatemore »
-
This study presents the role of 5d orbitals in the bonding, and electronic and magnetic structure of Ce imido and oxo complexes synthesized with a tris(hydroxylaminato) [((2- t BuNO)C 6 H 4 CH 2 ) 3 N] 3− (TriNO x 3− ) ligand framework, including the reported synthesis and characterization of two new alkali metal-capped Ce oxo species. X-ray spectroscopy measurements reveal that the imido and oxo materials exhibit an intermediate valent ground state of the Ce, displaying hallmark features in the Ce L III absorption of partial f-orbital occupancy that are relatively constant for all measured compounds. These spectra feature a double peak consistent with other formal Ce( iv ) compounds. Magnetic susceptibility measurements reveal enhanced levels of temperature-independent paramagnetism (TIP). In contrast to systems with direct bonding to an aromatic ligand, no clear correlation between the level of TIP and f-orbital occupancy is observed. CASSCF calculations defy a conventional van Vleck explanation of the TIP, indicating a single-reference ground state with no low-lying triplet excited state, despite accurately predicting the measured values of f-orbital occupancy. The calculations do, however, predict strong 4f/5d hybridization. In fact, within these complexes, despite having similar f-orbital occupancies and therefore levels of 4f/5dmore »