Dataset Information

Fac-Bis(acetonitrile-?N)tricarbonyl-(trifluoro-acetato-?O)rhenium(I).

ABSTRACT: In the title compound, [Re(CF(3)COO)(CH(3)CN)(2)(CO)(3)], the Re atom has a distorted octa-hedral configuration. The two acetonitrile mol-ecules and two of the three carbonyl groups occupy the equatorial plane of the complex, with the third carbonyl ligand and the trifluoroacetato ligand in the axial positions. The three carbonyl ligands are arranged in a fac configuration around the Re atom. The CF(3) segment of the trifluoroacetato ligand shows rotational disorder and the refined site-occupancy factors of the disordered parts are ca 0.5/0.5. The crystal structure is stabilized by C-H?O and C-H?F hydrogen bonds.

SUBMITTER: Kia R

PROVIDER: S-EPMC2959409 | biostudies-literature | 2008 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

fac-Bis(acetonitrile-κN)tricarbonyl-(trifluoro-acetato-κO)rhenium(I).

Kia Reza R Fun Hoong-Kun HK

Acta crystallographica. Section E, Structure reports online 20080924 Pt 10

In the title compound, [Re(CF(3)COO)(CH(3)CN)(2)(CO)(3)], the Re atom has a distorted octa-hedral configuration. The two acetonitrile mol-ecules and two of the three carbonyl groups occupy the equatorial plane of the complex, with the third carbonyl ligand and the trifluoroacetato ligand in the axial positions. The three carbonyl ligands are arranged in a fac configuration around the Re atom. The CF(3) segment of the trifluoroacetato ligand shows rotational disorder and the refined site-occupanc ...[more]

PMID: 21201050

Similar Datasets

Project description:The excellent π-accepting azodicarboxylic esters adcOR (R = Et, iPr, tBu, Bn (CH2-C6H5) and Ph) and the piperidinyl amide derivative adcpip were used as bridging chelate ligands in dinuclear Re(CO)3 complexes [{Re(CO)3Cl}2(µ-adcOR)] and [{Re(CO)3Cl}2(µ-adcpip)]. From the adcpip ligand the mononuclear derivatives [Re(CO)3Cl(adcpip)] and [Re(CO)3(PPh3)(µ-adcpip)]Cl were also obtained. Optimised geometries from density functional theory (DFT) calculations show syn and anti isomers for the dinuclear fac-Re(CO)3 complexes at slightly different energies but they were not distinguishable from experimental IR or UV-Vis absorption spectroscopy. The electrochemistry of the adc complexes showed reduction potentials slightly below 0.0 V vs. the ferrocene/ferrocenium couple. Attempts to generate the radicals [{Re(CO)3Cl}2(µ-adcOR)]•- failed as they are inherently unstable, losing very probably first the Cl- coligand and then rapidly cleaving one [Re(CO)3] fragment. Consequently, we found signals in EPR very probably due to mononuclear radical complexes [Re(CO)3(solv)(adc)]•. The underlying Cl-→solvent exchange was modelled for the mononuclear [Re(CO)3Cl(adcpip)] using DFT calculations and showed a markedly enhanced Re-Cl labilisation for the reduced compared with the neutral complex. Both the easy reduction with potentials ranging roughly from -0.2 to -0.1 V for the adc ligands and the low-energy NIR absorptions in the 700 to 850 nm range place the adc ligands with their lowest-lying π* orbital being localised on the azo function, amongst comparable bridging chelate N^N coordinating ligands with low-lying π* orbitals of central azo, tetrazine or pyrazine functions. Comparative (TD)DFT-calculations on the Re(CO)3Cl complexes of the adcpip ligand using the quite established basis set and functionals M06-2X/def2TZVP/LANL2DZ/CPCM(THF) and the more advanced TPSSh/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) for single-point calculations with BP86/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) optimised geometries showed a markedly better agreement of the latter with the experimental XRD, IR and UV-Vis absorption data.

Dataset Information

Fac-Bis(acetonitrile-?N)tricarbonyl-(trifluoro-acetato-?O)rhenium(I).

Publications

fac-Bis(acetonitrile-κN)tricarbonyl-(trifluoro-acetato-κO)rhenium(I).

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets