Synthesis and characterization of oxorhenium(V)-catecholate complexes. Crystal and molecular structures of (CH3)4N[ReO (O2C6H4)2] and (CH3)4N[ReO(PPh3) (O2C6H4)2]·CH3OH

Kettler, Peter B.; Chang, Yuanda; Zubieta, Jon; Abrams, Michael J.

doi:10.1016/0020-1693(94)03809-0

Cited by 25 publications

(26 citation statements)

References 16 publications

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“…The MOS values were also estimated for two of the previously mentioned dioxolene complexes and were found to be −2.1 ± 0.2 for both catecholate ligands of [ReO(Cat) 2 PPh 3 ] − complex ( 2 ) and − 1 ± 0.2 for the β‐lapachone ligand of ReCl 3 (SQ)PPh 3 complex ( 3 ). Thus, the estimated MOS are close to the integer values and coincide well with the proposed localized oxidation states …”

Section: Introductionsupporting

confidence: 81%

“…In the case of CASSCF/CASPT2, HF and DFT calculations, the geometries of 2 and 3 reported previously were used (Figure ). In the case of the CASSCF/NEVPT2 calculations, the geometries of 2 and 3 were slightly modified, namely, the phenyl groups in the PPh 3 ligand were replaced by methyl ones.…”

Section: Methodsmentioning

confidence: 99%

“…Noticeably less attention has been paid to the dioxolene complexes with the transition metals of the second and third rows. Among them, the rhenium complexes have attracted significant attention, most likely, because rhenium displays a wide range of accessible and stable oxidation states (from Re[I] to Re[VII]), which favors noninnocent behavior . Most of dioxolene ligands were derived from 1,2‐benzoquinone (Q) and its 3,5‐di‐ tert ‐butyl substituted analogue (DTBQ).…”

Section: Introductionmentioning

confidence: 99%

“…Most of dioxolene ligands were derived from 1,2‐benzoquinone (Q) and its 3,5‐di‐ tert ‐butyl substituted analogue (DTBQ). Both the semiquinolate (eg, Re I (CO) 3 (PPh 3 )(DTBSQ) and [Re IV Cl 3 (SQ)PPh 3 ]) and catecholate ([Re VI (DBTCat) 3 ], (NEt 4 )[Re VII O 2 (DTBCat) 2 ], (NEt 4 )[Re V O(DTBCat) 2 ], (HNEt 3 )(NBu 4 )[ReCl 4 (Cat)], (NMe 4 )[ReO(Cat) 2 PPh 3 ]) types of complexes were reported. The assignment of the oxidation states was mainly performed based on the XRD structures of these complexes, in some cases, the EPR spectra were also recorded.…”

Section: Introductionmentioning

confidence: 99%

“…Molecular structures of complexes 1 ‐ 3 according to the XRD data of Refs (the hydrogen atoms are omitted for clarity)…”

Section: Introductionmentioning

confidence: 99%

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Ab initio and density functional theory study of the electronic structure of rhenium complexes with noninnocent dioxolene ligands: Localized vs delocalized valence states

Dmitriev

Gritsan

2019

Int J of Quantum Chemistry

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The dioxolene type ligands (Diox) derived from ortho-quinones are the most widely studied redox noninnocent ligands existing in the dianionic (Cat), anion radical (SQ) or neutral (Q) forms although a highly delocalized electronic structure is also possible. For [ReO(Diox) 2 PPh 3 ] − (2) and [ReCl 3 (Diox)PPh 3 ] (3) complexes, the Re V -Cat 2 and Re IV -SQ localized valence states were proposed on the basis of their XRD structures. To understand in detail the electronic structure of these complexes, we performed a series of the all-electron calculations at the DKH2-CASSCF/CASPT2 and DKH2-CASSCF/NEVPT2 levels taking into account scalar relativistic and spin-orbit effects. All calculations predicted that 2 has a singlet ground state with a predominant contribution of a single electronic configuration with doubly occupied molecular orbitals being pure o-quinone LUMOs of both Diox ligands that corresponds to the Re V -Cat 2 valence state. Complex 3 has a triplet ground state with four electronic configurations contributing mainly into its wavefunction and differing by the occupation of bonding and antibonding combinations of the o-quinone LUMO and rhenium d-AO with nearly equal contributions. This leads to the empirical "metrical oxidation state" of dioxolene ligand being −1 that is usually referred to the Re IV -SQ oxidation state. However, in fact, the negative charge on the Diox ligand is mainly provided by a pair of electrons on the bonding MO. The standard DFT calculations entirely fail to correctly predict the ground state multiplicity for 3. K E Y W O R D S DFT and CASSCF, dioxolene ligands, electronic structure, metrical oxidation state, rhenium complexes 1 | INTRODUCTIONIn the recent years, redox noninnocent ligands have attracted much attention in coordination and organometallic chemistry. [1,2] These are the ligands, whose oxidation state in the metal complex is ambiguous and, thus, the actual oxidation state of the metal center in such complexes may differ from the formal one. Redox noninnocent ligands can serve as reservoirs for electrons, which allows one to perform many-electron transformations of metals that are impossible under other conditions. Such complexes are very wide-spread and comprise a huge variety of metal centers: namely, from the first raw transition metals to actinides. [1][2][3][4] Among them, the transition metal complexes of redox noninnocent ligands are of particular interest because of their biological importance, [5] catalytic activity, [6] and unusual magnetic properties. [7] The number of redox noninnocent ligands is also very large and includes both the small molecular species (NO and O 2 ) and a number of chelating ligands, for example, pyridine-2,6-diimines, ortho-iminoquinones, α-diimines, amidophenolates, and so forth. [1,2] The most well-known redox

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Section: Introductionsupporting

confidence: 81%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Molecular structures of complexes 1 ‐ 3 according to the XRD data of Refs (the hydrogen atoms are omitted for clarity)…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ab initio and density functional theory study of the electronic structure of rhenium complexes with noninnocent dioxolene ligands: Localized vs delocalized valence states

Dmitriev

Gritsan

2019

Int J of Quantum Chemistry

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Oxorhenium(V) Complexes of Carbohydrate Ligands

Klüfers

Krotz

Oßberger

2002

Eur. J. Inorg. Chem.

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The reaction of anhydroerythritol (AnEryt) and methyl-β-Dgalactopyranoside (Me-β-D-Galp) with dichloro[hydridotris-(pyrazolyl)borato]oxorhenium(V) [(tpb)ReOCl 2 ] in methanol/ triethylamine results in the formation of blue crystals of the diolato complexes [(tpb)ReO(AnErytH −2 )] (1) and [(tpb)Re-O(Me-β-D-Galp3,4H −2 )] (2). The amounts of anti-1 and syn-1 isomers are investigated by means of NMR spectroscopy and depend on the solvent chosen. For 2, the generally rigid pyr-

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Binding of Catechols to Iron(III)–Octaethylporphyrin: An Experimental and DFT Investigation

2010

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Cutting carbons: The three‐dimensional structure of polyneuridine aldehyde esterase (PNAE) gives insight into the enzymatic mechanism of the biosynthesis of C9‐ from C10‐monoterpenoid indole alkaloids (see scheme). PNAE is a very substrate‐specific serine esterase. It harbors the catalytic triad S87‐D216‐H244, and is a new member of the α/β‐fold hydrolase superfamily. Its novel function leads to the diversification of alkaloid structures.

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Synthesis and characterization of oxorhenium(V)-catecholate complexes. Crystal and molecular structures of (CH3)4N[ReO (O2C6H4)2] and (CH3)4N[ReO(PPh3) (O2C6H4)2]·CH3OH

Cited by 25 publications

References 16 publications

Ab initio and density functional theory study of the electronic structure of rhenium complexes with noninnocent dioxolene ligands: Localized vs delocalized valence states

Ab initio and density functional theory study of the electronic structure of rhenium complexes with noninnocent dioxolene ligands: Localized vs delocalized valence states

Oxorhenium(V) Complexes of Carbohydrate Ligands

Binding of Catechols to Iron(III)–Octaethylporphyrin: An Experimental and DFT Investigation

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