Force constants and vibration frequencies of the rhenium-oxygen bonds in the infrared region (200–4000 cm−1)

Jeżowska‐Trzebiatowska, B.; Hanuza, J.; Baluka, M.

doi:10.1016/0584-8539(71)80229-5

Cited by 41 publications

(21 citation statements)

References 52 publications

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“…In the non-stoichiometric phases with 1 ,2-Me,Im, besides the normal [~eo,L,],+ band at 78 1 cm-I, the red-violet crystals give a broader feature at 932 cm-' for the v(Re=O) mode of [R~o(oH)L,]~+. The similar band for the protonated species was observed at 981 cm-' for ethylenediamine (30) and 969 cm-' for cyclam (33). Also present in the sample obtained by method 1 (form 11) is a band at 907 cm-', due to uncoordinated ReO,-acting as the counterion for the [R~o(oH)L,]~+ formed.…”

Section: Discussionsupporting

confidence: 49%

“…The strong v,,(O=Re=O) band, observed at -820 cm-' for the pyridine and ethylenediarnine analogues (30), is clearly shifted below 800 cm-' in the imidazole complexes, but assignment is not straightforward, since the ligands also show strong y(C-H) bands in this region. Furthermore, the y(N-H) mode of free ImH at -950 cm-' is known to move to the 700-850 cm-' range in various complexes (29,31,32), mainly because of changes in hydrogen bonding.…”

Section: Discussionmentioning

confidence: 99%

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Non-stoichiometric chloride salts of dioxotetrakis(imidazole)rhenium(V) cations

Lebuis¹,

Young²,

Beauchamp³

1993

Can. J. Chem.

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. Orange [Re02L4]C1 salts were prepared with L = imidazole and 2-methylimidazole. The presence of a strong Re=O stretching band in the infrared spectra near 785 cm-I is consistent with a trans-dioxo octahedral structure. With 1,2-dimethylimidazole, red-violet solids were obtained, which were studied by X-ray diffraction. Form I (from methanol): cubic, l a j d , a = 25.205 A, R = 0.032, 986 observed reflections; form I1 (from ethanol-dichloromethane): cubic, Ia3d, a = 25.520 A, R = 0.056, 766 observed reflections. Both materials are non-stoichiometric, containing trans-[R~O,L,]+ and protonated t r a n s -[~e~(~~) L~]~+ in an approximate ratio of 3: 1 for I and 2: 1 for 11. In both cases, the unit cell contains 1 "normal" C1-ion and 2/3 H 2 0 per complex. In form I, the additional charge of [ReO(OH)L412+ is balanced by an extra C1-ion partly occupying the unit cell origin, where it is replaced by disordered methanol the rest of the time. In form 11, Re04-and CH2Cl2 play the corresponding roles. In the infrared spectra, besides the characteristic band for the dioxo species, both forms show an extra peak at -932 cm-' originating from the protonated species, whereas form I1 shows an additional band at 907 cm-' for uncoordinated Re04-. The 'H and "C NMR spectra of both forms in D 2 0 are identical to those of the pure [R~O~L,]' salt, indicating that the protonated species is strongly acidic. ANNE-MARIE LEBUIS

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Section: Discussionsupporting

confidence: 49%

Section: Discussionmentioning

confidence: 99%

Non-stoichiometric chloride salts of dioxotetrakis(imidazole)rhenium(V) cations

Lebuis¹,

Young²,

Beauchamp³

1993

Can. J. Chem.

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“…In 4a and 46, the trans-dioxo unit shows a single v,,(O=Re=O) band at 795 cm-', halfway between those found for [R~o,(cN),]~-(775 cm-I) (34) The crystals contain roughly octahedral molecules of the trans-trans isomer (Fig. l), in which the neutral azaindole ligand is coordinated via N(7).…”

Section: Infrared Spectroscopymentioning

confidence: 99%

Preparation and structure of oxo-rhenium(V) complexes with 7-azaindole

Lebuis¹,

Beauchamp²

1993

Can. J. Chem.

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ANNE-MARIE LEBUIS and ANDRE L. BEAUCHAMP. Can. J . Chem. 71, 2060Chem. 71, (1993. Four Re(V) 0x0 compounds were obtained from 7-azaindole (Haza) and ReOCI, (PPh,),: the 0x0-bridged dimer Re,0,Cl,(Ha~a)~ (I), the 0x0-ethoxo lnonomers ReO(OEt)CI,(Haza), (2) and ReO(OEt)Clz(Haza)(PPh3) (3), and the dioxo [ReO,(Ha~a) Introduction mono and dioxo complexes of Re(V) with pyridine and reIn many of the complexes formed by 7-azaindole2 (Haza) lated ligands, have attracted increasing attention in connec-(I), the monoanion plays a bidentate bridging role in dinution with electron (17) and 0x0 (18) transfer reactions. These compounds exhibit interesting electrochemical (19) and ex-

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“…Die Stamm Verbindung, das Kaliumosmat(VI), wurde lange Zeit als K2[0s04] • 2 H20 formuliert bis durch spektroskopische Untersuchungen und durch Röntgenstruktur-analyse die oktaedrische Koordination des Zentralions und damit die Formel £raw<s-K2[0s02(0H)4] gesichert war [2][3][4][5]. Typisch für die Verbindungsklasse sind die deutlich kürzeren Bindungsabstände der axialen Dioxogruppierung als Folge starker jr-Donorbindungen der O-Atome und der stets gefundene Diamagnetismus, der auf einen SingulettGrundzustand am sechswertigen Osmium (d 2 ) hinweist.…”

Section: Introductionunclassified

Die Schwingungsfeinstruktur der elektronischen Absorptionsspektren von [OsO₂(ox)₂]²-und [OsO₂(mal)₂]^2-/ Vibrational Fine Structure on the Electronic Absorption Spectra of [OsO₂(ox)₂]^2-and [OsO₂(mal)₂]^2-

Preetz

Schulz

1983

Zeitschrift Für Naturforschung B

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AbstractThe complexes (TBA)2[OsO2(ox)2] and (TBA)2[OsO2(mal)2] have been prepared and characterized. The IR and Raman frequencies are assigned according to point group D2h. The electronic absorption spectra measured on thin films of the solid complex salts on silica discs at 10 K show well resolved vibrational fine structure. Two very weak bands (ε: 4-58) in the visible region are assigned to d-d transitions from the singlet ground state ag2 (dxy) to a triplet and singlet term of the equivalent π* orbitals b2g/b3g (dxz, dyz). The two more intense band systems (ε: 500-1500) in the UV region are attributed to CT transitions from b2u/b3u π orbitals of the oxo ligands to the lowest unoccupied orbitals b2g/b3g of the central ion. These electronic transitions couple with vs(Os = O) as indicated by the main progression of about 700 cm-1 . In comparison to the vibrational ground state this lowered frequency is caused by population of antibonding π levels. The loosening of the Os = O bonds in the excited state is demonstrated by high anharmonic constants (-2.5 to -10.5 cm-1) and the estimated bond lengthening of about 12 pm. Moreover the vibrational fine structure of the malonato complex shows many combination modes of vs(Os = O) with other symmetric fundamentals. Due to lower site symmetry in the solid state the CT transitions of the malonato compound are split into 2 components with a spacing of about 200 cm-1 .

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Force constants and vibration frequencies of the rhenium-oxygen bonds in the infrared region (200–4000 cm−1)

Cited by 41 publications

References 52 publications

Non-stoichiometric chloride salts of dioxotetrakis(imidazole)rhenium(V) cations

Non-stoichiometric chloride salts of dioxotetrakis(imidazole)rhenium(V) cations

Preparation and structure of oxo-rhenium(V) complexes with 7-azaindole

Die Schwingungsfeinstruktur der elektronischen Absorptionsspektren von [OsO₂(ox)₂]²-und [OsO₂(mal)₂]^2-/ Vibrational Fine Structure on the Electronic Absorption Spectra of [OsO₂(ox)₂]^2-and [OsO₂(mal)₂]^2-

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Force constants and vibration frequencies of the rhenium-oxygen bonds in the infrared region (200–4000 cm−1)

Cited by 41 publications

References 52 publications

Non-stoichiometric chloride salts of dioxotetrakis(imidazole)rhenium(V) cations

Non-stoichiometric chloride salts of dioxotetrakis(imidazole)rhenium(V) cations

Preparation and structure of oxo-rhenium(V) complexes with 7-azaindole

Die Schwingungsfeinstruktur der elektronischen Absorptionsspektren von [OsO2(ox)2]2 -und [OsO2(mal)2]2-/ Vibrational Fine Structure on the Electronic Absorption Spectra of [OsO2(ox)2]2-and [OsO2(mal)2]2-

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Die Schwingungsfeinstruktur der elektronischen Absorptionsspektren von [OsO₂(ox)₂]²-und [OsO₂(mal)₂]^2-/ Vibrational Fine Structure on the Electronic Absorption Spectra of [OsO₂(ox)₂]^2-and [OsO₂(mal)₂]^2-