Abstract:Die Kristall‐ (P21/b; Z=4) und Molekularstruktur der aus dem vierkernigen Komplex [Cu(OMe)(2,4,6‐C13C6 H2 O) (MeOH)]4 unter der Einwirkung äquimolarer Mengen von Chinolin entstehenden Titelverbindung werden röntgenographisch untersucht.
“…The C-O distance of 1.288 (6) Ä is comparable to those found in other chlorophenolate complexes (1.30-1.31 Ä) [1][2][3][4][5][6][7][8] and in the hydrogenbonded compounds of substituted amines with chlorophenols (1.30-1.31 Ä) [24], and is intermediate between the bond lengths for phenolate anions (1.26 Ä) [25] and ort/to-chlorophenols and their ethers (1.36-1.38 Ä) [26], The M-O-C angle, 125.4°, is in the range found in the other metal chlorophenolates, 121.7-133.4°. The C-Cl distance of the coordinated ort/io-chlorine atom (1.748 (6) Ä) is slightly longer than the C-Cl distance of the non-coordinated orthochlorine atom (1.729 (6) Ä), but is not significantly longer than the C-Cl distance of the para-chlorine atom (1.745 (7) Ä).…”
Section: Nqr Spectrasupporting
confidence: 79%
“…To accommodate metals such as silver that are larger than the fourth-period d-block metal ions, in Figure 2 we replot the available 35 C1 NQR data [33] as a function of the average excess of the metalchlorine distance over the normal bond distance for a terminal metal-inorganic chlorine bond [34]. (Ph 3 P) 2 AgOPhCl 3 fits in the middle of the range of the same correlation as the first-row transition-metal chlorophenolates [NQR frequency difference of CI 6 and CI 2 = 3.394-2.959 (excess distance) ±0.353, r = 0.938], and is comparable in frequency difference to the well-characterized copper(II) chlorophenolates [1,[3][4][5]29], There appears to be little correlation of the NQR frequency difference with the C-Cl-M bond angle ( Fig. 3; r = 0.781).…”
The crystal structure of (Ph 3 P) 2 AgOC 6 H 2 Cl 3 (I) is reported along with the syntheses and 35 C1 and 63 Cu NQR spectra of I and several related silver (I) and copper (I) 2,6-di-and 2,4,6-trichlorophenolates containing phosphines, phosphites, and pyridine as co-ligands. I crystallizes in space group P2 Jc with a= 16.692(4) Ä, b= 17.942 (4) A, c= 12.857 (3) Ä, /? = 97.60 (1)°, F = 3816.68 Ä 3 , and Z = 4. The final R (F) = 0.0475 and R (W) = 0.0396. Ag is coordinated in a trigonal planar geometry by the P atoms of the two triphenylphosphine ligands and the O atom of the chlorophenolate; Ag is then capped by one ortho-chlorine of the trichlorophenolate ligand at a distance of 3.160 (2) Ä. In the 35 C1 NQR spectrum of this compound the two orf/io-chlorines of the trichlorophenolate ligand have a large frequency difference of 1.500 MHz, indicating that one ortho-chlorine is coordinated to the silver; 35 C1 NQR spectra of related complexes are also presented and discussed. The 35 C1 NQR frequency differences of coordinated and non-coordinated orr/io-chlorines in metal chlorophenolates correlate well with the metal-chlorine distances but not with the metal-chlorine-carbon bond angles. A different correlation is found for the silver complexes of dichloroalkanes; possible reasons for this are discussed.
“…The C-O distance of 1.288 (6) Ä is comparable to those found in other chlorophenolate complexes (1.30-1.31 Ä) [1][2][3][4][5][6][7][8] and in the hydrogenbonded compounds of substituted amines with chlorophenols (1.30-1.31 Ä) [24], and is intermediate between the bond lengths for phenolate anions (1.26 Ä) [25] and ort/to-chlorophenols and their ethers (1.36-1.38 Ä) [26], The M-O-C angle, 125.4°, is in the range found in the other metal chlorophenolates, 121.7-133.4°. The C-Cl distance of the coordinated ort/io-chlorine atom (1.748 (6) Ä) is slightly longer than the C-Cl distance of the non-coordinated orthochlorine atom (1.729 (6) Ä), but is not significantly longer than the C-Cl distance of the para-chlorine atom (1.745 (7) Ä).…”
Section: Nqr Spectrasupporting
confidence: 79%
“…To accommodate metals such as silver that are larger than the fourth-period d-block metal ions, in Figure 2 we replot the available 35 C1 NQR data [33] as a function of the average excess of the metalchlorine distance over the normal bond distance for a terminal metal-inorganic chlorine bond [34]. (Ph 3 P) 2 AgOPhCl 3 fits in the middle of the range of the same correlation as the first-row transition-metal chlorophenolates [NQR frequency difference of CI 6 and CI 2 = 3.394-2.959 (excess distance) ±0.353, r = 0.938], and is comparable in frequency difference to the well-characterized copper(II) chlorophenolates [1,[3][4][5]29], There appears to be little correlation of the NQR frequency difference with the C-Cl-M bond angle ( Fig. 3; r = 0.781).…”
The crystal structure of (Ph 3 P) 2 AgOC 6 H 2 Cl 3 (I) is reported along with the syntheses and 35 C1 and 63 Cu NQR spectra of I and several related silver (I) and copper (I) 2,6-di-and 2,4,6-trichlorophenolates containing phosphines, phosphites, and pyridine as co-ligands. I crystallizes in space group P2 Jc with a= 16.692(4) Ä, b= 17.942 (4) A, c= 12.857 (3) Ä, /? = 97.60 (1)°, F = 3816.68 Ä 3 , and Z = 4. The final R (F) = 0.0475 and R (W) = 0.0396. Ag is coordinated in a trigonal planar geometry by the P atoms of the two triphenylphosphine ligands and the O atom of the chlorophenolate; Ag is then capped by one ortho-chlorine of the trichlorophenolate ligand at a distance of 3.160 (2) Ä. In the 35 C1 NQR spectrum of this compound the two orf/io-chlorines of the trichlorophenolate ligand have a large frequency difference of 1.500 MHz, indicating that one ortho-chlorine is coordinated to the silver; 35 C1 NQR spectra of related complexes are also presented and discussed. The 35 C1 NQR frequency differences of coordinated and non-coordinated orr/io-chlorines in metal chlorophenolates correlate well with the metal-chlorine distances but not with the metal-chlorine-carbon bond angles. A different correlation is found for the silver complexes of dichloroalkanes; possible reasons for this are discussed.
“… 3 Magnetic coupling constants (2 J ) for Cu(II) alkoxo-bridged complexes calculated with the B3LYP-bs method using a double-ζ basis set for model 3 changing the bridging hydroxo group for a methyl group as a function of bridging angle θ. The black circles correspond to the experimental values, ,,− and the solid lines give the calculated values (triangles) for the planar model (τ = 0°) and the squares for the model with τ = 40°. The uncircled labels indicate the value of τ for each experimental structure.…”
Magnetic coupling constants (2J) of hydroxo- and
alkoxo-bridged copper binuclear compounds have been
evaluated to determine the accuracy of different density functional
methods and to study the magnetic behavior of
these compounds. Comparison between the calculated and
experimental coupling constants for the complete
structures
of five compounds shows that the most successful computational strategy
is the combination of the B3LYP method
with the broken-symmetry approach. Calculations for model
compounds of both families yield reasonable
approximations to the values of magnetic coupling constants calculated
for the full molecular structures. Our
calculations show a correlation between the magnetic coupling constant
and the Cu−O−Cu bridging angle and with
the out-of-plane displacement of the hydroxo or alkoxo groups, in
agreement with the experimental data. The
counterions of the hydroxo-bridged complexes, when hydrogen bonded to
the bridging hydroxo group, determine
the extent of the out-of-plane displacement of its hydrogen atom and
strongly influence the sign and magnitude of
the magnetic interaction. The energy gap between the two singly
occupied molecular orbitals is shown to determine
the changes in the value of 2J for small structural
variations.
“…Figure 4 includes the gas-phase spectrum of Ga2Cl6 recorded with a 0.5-mm gold spacer between the window and the back-plate. 26 With a few exceptions, the liquid spectra are presented in emittance, «*, with opaque melts as references.…”
Section: Resultsmentioning
confidence: 99%
“…The binary salt mixtures LiAlCl4, LiAl2Cl7, KInCl4, and CsGa2Cl7 were obtained from previous spectroscopic work. 11,25,26 Two qualities of A1C13 were employed. For preparation of NaAlCl4, NaAl2Cl7, and NaAl3Cl10, Al chips, purity 99.998% (Vigeland Brug), reacted at 450 °C with a flow of dry HC1 from a HC1 generator (NaCl + H2S04).…”
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
