2006
DOI: 10.1002/zaac.200600062
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Azidoaurates of the Alkali Metals

Abstract: Synthesis, crystal structure as well as IR-and Ramanspectroscopic properties of the new ternary azidoaurates(III) A[Au(N 3 ) 4 ] (A ϭ K, Rb, Cs) are reported. The translucent orangered compounds were prepared by reaction of the respective binary azides with HAuCl 4 in aqueous solutions at room temperature. The crystal structures determined by single crystal X-ray diffraction methods are monoclinic 1671 and provide the first examples for azidoaurates with mono-atomic cations. The unusual reduction of the lattic… Show more

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Cited by 16 publications
(31 citation statements)
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“…The range 500–700 cm –1 is dominated by the in‐plane and out‐of‐plane deformation vibrations of the azido groups whereas the respective (N–N–N) stretching vibrations are registered as two separated sets of frequencies between 1200–1300 cm –1 and 1900–2100 cm –1 . The differences in the (N–N) wave numbers harmonize well with the measured bond lengths for the azidopalladate anions and the ELI calculations for [Au(N 3 ) 4 ] – 6, which indicates that the (N‐N) bonds for the outermost atoms in the azido groups ( – N –N c – N o ) are significantly shorter than those of the inner atoms ( –N i – N c –N). The respective stretching force constants follow the same order as for the bonds, with f (N–N) = 15.44 N · cm –1 and 10.18 N · cm –1 for the outermost and the inner (N–N) bonds, respectively.…”
Section: Resultssupporting
confidence: 75%
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“…The range 500–700 cm –1 is dominated by the in‐plane and out‐of‐plane deformation vibrations of the azido groups whereas the respective (N–N–N) stretching vibrations are registered as two separated sets of frequencies between 1200–1300 cm –1 and 1900–2100 cm –1 . The differences in the (N–N) wave numbers harmonize well with the measured bond lengths for the azidopalladate anions and the ELI calculations for [Au(N 3 ) 4 ] – 6, which indicates that the (N‐N) bonds for the outermost atoms in the azido groups ( – N –N c – N o ) are significantly shorter than those of the inner atoms ( –N i – N c –N). The respective stretching force constants follow the same order as for the bonds, with f (N–N) = 15.44 N · cm –1 and 10.18 N · cm –1 for the outermost and the inner (N–N) bonds, respectively.…”
Section: Resultssupporting
confidence: 75%
“…Using the force field and initial force constants values previously employed on [Au(N 3 ) 4 ] – 6, the following (N–N) and (Pd–N) stretching ( f ), bond interaction ( f ′), deformation ( f D ) and torsion (τ) force constants were calculated giving the best fit with the experimental frequencies obtained for 1 : f (N o –N c ) = 14.61 N · cm –1 , f (N i –N c ) = 10.92 N · cm –1 , f (Pd–N) = 2.41 N · cm –1 , f′ (N o –N i ) = 1.53 N · cm –1 , f D (N–N–N) = 0.60 N · cm, f D (N–Pd–N) = 0.82 N · cm, f D (N–N–Pd) = 0.63 N · cm, τ = 0.02 N · cm.…”
Section: Resultsmentioning
confidence: 99%
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“…The raw ELI-D (and ELF) disynaptic bond basin populations are not directly related to the formal bond order derived from the difference between the number of occupied bonding and antibonding MOs. It was shown, that usage of a suitable reference system may yield effective bond orders, which are consistent with interatomic force constants from lattice dynamical models fitted to experimental vibrational spectra [40]. We choose CaC 2 (tetragonal crystal structure from [41]) as the prototype compound for a C 2 2À unit.…”
Section: Article In Pressmentioning
confidence: 91%
“…Moreover, there are found 0.8e À more in the lone pair type basins and 0.6e À less in the bonding basin. Calculating a type of effective bond order from the ratio between the bond basin populations of the reference and the actual C 2 unit [40] yields 3 Â 2.56/3.25 ¼ 2.4, which is roughly the same as obtained from COHP analysis. Thus, although topologically there is only one lone pair type of attractor for each C atom of the C 2 species as in CaC 2 , the present C 2 species displays an effective bond order between that of the C 2 2À and the C 2 4À unit.…”
Section: Article In Pressmentioning
confidence: 98%