“…The last two distances are essentially the same within experimental error. In the quadruply bonded Tc 2 6+ molecule Tc 2 (O 2 CCH 3 ) 4 Cl 2 , the Tc−Tc bond distance of 2.192(1) Å is longer by 0.05 Å than that of 2.1260(5) Å in the Tc 2 5+ anion [Tc 2 (O 2 CCH 3 ) 4 Cl 2 ] - , which has a formal bond order of 3.5. , 1 Structure of 1-PF 6 showing how the PF 6 anion rests above the pocket formed by the p -anisyl groups at a long distance from the Pd 2 5+ unit. Displacement ellipsoids (anisotropic for the cation and isotropic for the anion) are drawn at the 30% probability level.…”
Reaction of Pd(2)(DAniF)(4), 1, (DAniF = di-p-anisylformamidinate) with 1 equiv of AgPF(6) in CH(2)Cl(2) at or below -10 degrees C produces the paramagnetic species [Pd(2)(DAniF)4]PF(6), 1-PF(6), that has been studied by X-ray crystallography, UV-vis spectroscopy, electrochemistry, and multifrequency (9.5, 34.5, 110, and 220 GHz) EPR spectroscopy. Upon oxidation of the precursor, the Pd-Pd distance decreases by 0.052 Angstrom from 2.6486(8) to 2.597(1) Angstrom. The EPR spectra show broad signals with line widths of about 1000 G. The spectra collected at high field show a large spread of g tensor components ( approximately 0.03), but these are masked at lower frequencies (9.5 and 34.5 GHz). A reinvestigation using high-field EPR of the p-tolyl analogue, which is the only other structurally characterized Pd(2)(5+) species (Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J. Am. Chem. Soc. 1988, 110, 1144), shows that this species, which had been reported to give an isotropic 9.5 GHz EPR spectrum, also gives anisotropic 110 and 220 GHz EPR spectra with a similarly large spread of g tensor components consistent with the unpaired electron residing in a metal-based MO. The results of these studies and calculations using density functional theory are consistent with the oxidation being metal-based, resulting in an uncommon Pd(2)(5+) species with a Pd-Pd bond order of 1/2.
“…The last two distances are essentially the same within experimental error. In the quadruply bonded Tc 2 6+ molecule Tc 2 (O 2 CCH 3 ) 4 Cl 2 , the Tc−Tc bond distance of 2.192(1) Å is longer by 0.05 Å than that of 2.1260(5) Å in the Tc 2 5+ anion [Tc 2 (O 2 CCH 3 ) 4 Cl 2 ] - , which has a formal bond order of 3.5. , 1 Structure of 1-PF 6 showing how the PF 6 anion rests above the pocket formed by the p -anisyl groups at a long distance from the Pd 2 5+ unit. Displacement ellipsoids (anisotropic for the cation and isotropic for the anion) are drawn at the 30% probability level.…”
Reaction of Pd(2)(DAniF)(4), 1, (DAniF = di-p-anisylformamidinate) with 1 equiv of AgPF(6) in CH(2)Cl(2) at or below -10 degrees C produces the paramagnetic species [Pd(2)(DAniF)4]PF(6), 1-PF(6), that has been studied by X-ray crystallography, UV-vis spectroscopy, electrochemistry, and multifrequency (9.5, 34.5, 110, and 220 GHz) EPR spectroscopy. Upon oxidation of the precursor, the Pd-Pd distance decreases by 0.052 Angstrom from 2.6486(8) to 2.597(1) Angstrom. The EPR spectra show broad signals with line widths of about 1000 G. The spectra collected at high field show a large spread of g tensor components ( approximately 0.03), but these are masked at lower frequencies (9.5 and 34.5 GHz). A reinvestigation using high-field EPR of the p-tolyl analogue, which is the only other structurally characterized Pd(2)(5+) species (Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J. Am. Chem. Soc. 1988, 110, 1144), shows that this species, which had been reported to give an isotropic 9.5 GHz EPR spectrum, also gives anisotropic 110 and 220 GHz EPR spectra with a similarly large spread of g tensor components consistent with the unpaired electron residing in a metal-based MO. The results of these studies and calculations using density functional theory are consistent with the oxidation being metal-based, resulting in an uncommon Pd(2)(5+) species with a Pd-Pd bond order of 1/2.
“…Some closely related patterns were found, e.g. one containing the ( 2 -acetato)-hexachloridodirhenate anion exhibiting the same structure of the title compound (Vega et al, 2002), and one containing the di-2 -acetato-bis(dibromidorhenate) anion (Koz'min et al, 1981).…”
The crystal structure of a binuclear monocarboxylato dirhenium(III) complex with a fulvalene derivative is reported. This compound represents a radical cation salt containing a cluster unit with rhenium–rhenium quadruple bond.
“…The space groups C2, Cc, and C2/c are consistent with these extinctions. Of the 2683 independent reflections in the range 0 < 29 < 50°, 1631 having I > 2<r (7) were used to solve and refine the structure.…”
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