Synthesis, infrared spectra, magnetic properties, and electronic structure of di-.mu.-oxo- and di-.mu.-oxo-bis(di-.mu.-oxo)-bridged oxomolybdates(V) and their theoretical interpretation

Jeżowska‐Trzebiatowska, B.; Rudolf, Mikołaj F.; Natkaniec, L.; Sabat, H.

doi:10.1021/ic50133a023

Cited by 39 publications

(8 citation statements)

References 30 publications

(1 reference statement)

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“…12 They assigned a vibrational band at ∼380 cm -1 as the symmetric Mo-O-Mo stretching of a linear bridge. However, their suggestion "The greater than expected 18 O-isotope shift for a linearly bridged system could suggest that the predicted C 2h or C 2V symmetry of the Mo 2 O 3 2+ species in 6 M HCl may not hold perfectly in solution" 12 is consistent with the current EXAFS results.…”

Section: Modosupporting

confidence: 80%

“…63,64 Our ADF calculations for the ground-state electronic structure of the [Mo 2 O 4 Cl 4 (trans-H 2 O) 2 ] 2complex of 3 show that the HOMO (75A), which has a significant amount (∼55%) of Mo(4d xy ) character, is occupied with two electrons due to the Mo-Mo bond formation. 18 The LUMO (76A) and LUMO+1 (77A), both with more than 50% mixed 4d xz and 4d yz character, are almost degenerate with only 0.2 eV energy difference (see Figure 10). Therefore, the first intense peak observed in the L 2,3 -edge XANES spectra of 3 should correspond to the transition: Mo (2p) f [76A, 77A (d xz , d yz )] (cf.…”

Section: Structural Characterization Of Mo(v) Speciesmentioning

confidence: 99%

“…11 Lincoln and Loehr combined electronic and vibrational spectroscopy to study the hydrolysis of Mo(V) in HCl. They measured Raman spectra of 0.05-0.54 M Mo(V) solutions in 10 M HCl, 0.163 M Mo(V) in 6 M HCl, and 0.05 M Mo(V) in 2 M HCl, using 18 O-isotopic substitution to aid assignments of Raman bands measured at 90 and 300 K, and concluded that the major Mo(V) species in 10, 5-6, and 2 M HCl solutions were represented by the structures a, c, and f (Figure 1), respectively. 12 The Raman band at ∼380 cm -1 was assigned as the symmetric Mo-O-Mo stretching for [Mo 2 O 3 Cl 8 ] 4-(Figure 1c), supporting a linear Mo-O-Mo entity.…”

Section: Introductionmentioning

confidence: 99%

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Structural Characterization of Molybdenum(V) Species in Aqueous HCl Solutions

et al. 2007

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Mo(V) aqua-chloro complexes in hydrochloric acid solutions have been studied by means of Mo K- and L2,3-edge X-ray absorption and Raman spectroscopic methods. The solid compounds (HPPh3)2[MoOCl5] (1), 6[MoOCl4(H2O)]-.10(pyH)+.4Cl- (2), and (pyH)2[Mo2O4Cl4(trans-OH2)2] (3) were used for structural comparisons. The compound 2 crystallizes in the orthorhombic space group Pmma (no. 51) with a=21.398(3), b=8.057(4), c=13.330(4) A, and Z=4. In 0.2 M solutions of MoCl5 in 7.4-9.4 M HCl the mononuclear [MoOCl4(OH2)]- complex dominates with the bond distances Mo=O 1.66(2) A, Mo-Cl 2.38(2) A, and Mo-OH2 2.30(2) A. Its Raman band at 994 cm-1 for the Mo=O symmetric stretching vibration is closer to that of 2 (988 cm-1) than of 1 (969 cm-1). The Mo K-edge EXAFS spectrum for 0.2 M MoCl5 in 1.7 M HCl solution reveals a dinuclear [Mo2O4Cl6-n(OH2)n]n-4 (n=2, 3) complex with a double oxygen bridge and the average distances Mo=O 1.67(2) A, Mo-(mu-O) 1.93(2) A, Mo-Cl 2.47(3) A, Mo-Mo 2.56(2) A, and a short Mo-OH2 distance of 2.15(2) A, which implies that at least one of the aqua ligands is in equatorial position relative to the two axial Mo=O bonds. This position differs from the Mo-OH2 configuration exclusively trans to the M=O groups of the isomeric (with n=2) dinuclear complex in 3. The difference in the ligand field is also reflected in their L2,3-edge XANES spectra. For 0.2 M MoCl5 solutions in intermediate HCl concentrations (3.7-6.3 M) the Raman bands at 802 cm-1 (Mo-O-Mo) and 738 cm-1 (Mo-(mu-O)2-Mo) verify three coexisting classes of Mo(V) complexes: mononuclear complexes together with dinuclear mono-oxo (e.g., [Mo2O3Cl6(H2O)2]2-) and dioxo bridged species, even though principal component analysis (PCA) of the corresponding series of EXAFS spectra only could distinguish two major components. By fitting linear combinations of the appropriate EXAFS oscillation components, dioxo-bridged dinuclear complexes were found to dominate at HCl concentrations

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Section: Modosupporting

confidence: 80%

Section: Structural Characterization Of Mo(v) Speciesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural Characterization of Molybdenum(V) Species in Aqueous HCl Solutions

et al. 2007

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“…The Tc-Tc distances of 2.543( 1) and 2.542(2) 8, for complexes 1 and 2 respectively are shorter than that of 2.580( 1) 8, for the Mo-Mo bond reported in the complex [(MoO(S,CNEt,)),-(p-O),]. The acute Tc-0-Tc angles and the relatively short Tc-Tc distances indicate the presence of a metal-metal single bond, which is consistent with the results of molecular orbital calculations for molybdenum systems 35 and the absence of ESR signals from 1 and 2. The Tc-Tc distances for both complexes are significantly longer than the average Tc-Tc distance of 2.365(1) 8, for a variety of di-p-oxo Tc" or Tc'~/Tc"' dimers (Table 9) where metal-metal multiple bonding has been proposed.…”

Section: Resultssupporting

confidence: 83%

Synthesis and structure of di-µ-oxo nitridotechnetium(VI) dimers and a monomeric nitridotechnetium(V) mixed-ligand complex

Baldas¹,

Boas²,

Colmanet³

et al. 1992

J. Chem. Soc., Dalton Trans.

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“…Pyridinium di-p-oxo bis(oxo-tetrakis-(isothiocyanate) molybdate (V)), (PyrH)4(Moz03(NCS)8), was prepared as reported [5,6] and characterized by its uv-visible spectrum.…”

Section: Methodsmentioning

confidence: 99%

The flash photolysis of di‐μ‐oxo‐bis(oxo‐molybdate(V)) acid aqueous solutions in the presence of excess thiocyanate

Martire

González

Feliz

et al. 1991

Int J of Chemical Kinetics

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The flash photolysis of the mono and di-thiocyanate complexes of @-ox0 bis(oxomolybdenum(V)) ( M O~O~( N C S ) , ( H~O )~_~~~~" where x = 1,2) has been studied in the system composed of perchloric acid solutions of M O~O~( H~O )~~~ in the presence of excess thiocyanate. Irradiation with light in the wavelength range 250-340 nm induced the formation of three reaction intermediates identified as p-0x0-bis (0x0-molybdenum(V)) species: Mo203( HZO): ' (A), Mo203(NCS) (H20):' ( B ) , and M O~O~( N C S )~( H~O )~~' (C).A rapid equilibria between the transient species is established before they decay following a first order kinetics. Intermediate A is the only species effective in promoting the observed decay leading to the end products Mo(V1) and Hz.The relative absorption spectrum of species A, B, and C are reported, as well as the measured stability constants for the formation of B and C in the temperature range 20-45°C. An overall mechanism is proposed.

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Synthesis, infrared spectra, magnetic properties, and electronic structure of di-.mu.-oxo- and di-.mu.-oxo-bis(di-.mu.-oxo)-bridged oxomolybdates(V) and their theoretical interpretation

Cited by 39 publications

References 30 publications

Structural Characterization of Molybdenum(V) Species in Aqueous HCl Solutions

Structural Characterization of Molybdenum(V) Species in Aqueous HCl Solutions

Synthesis and structure of di-µ-oxo nitridotechnetium(VI) dimers and a monomeric nitridotechnetium(V) mixed-ligand complex

The flash photolysis of di‐μ‐oxo‐bis(oxo‐molybdate(V)) acid aqueous solutions in the presence of excess thiocyanate

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