Reactivity of ([eta][sup 7]-cycloheptatrienyl)([eta][sup 5]-cyclopentadienyl)M (M = Ti, Nb) toward dithioacetic acid: Preparation and characterization of ([eta][sup 5]-C[sub 5]H[sub 5])Ti(S[sub 2]CCH[sub 3])[sub 3] and ([eta][sup 5]-C[sub 5]H[sub 5])Nb([eta][sup 2]-S[sub 2])(S[sub 2]CCH[sub 3])[sub 2]
- Cleveland State Univ., OH (United States) National Aeronautics and Space Administration, Cleveland, OH (United States)
- Cleveland State Univ., OH (United States)
A method for the high-yield syntheses (up to 85%) of the two new compounds ([eta][sup 5]-C[sub 5]H[sub 5])Ti(S[sub 2]CCH[sub 3])[sub 3] (1) and ([eta][sup 5]-C[sub 5]H[sub 5])Nb([eta][sup 2]-S[sub 2])(S[sub 2]CCH[sub 3])[sub 2] (2) from ([eta][sup 7]-C[sub 7]H[sub 7])M([eta][sup 5]-C[sub 5]H[sub 5]) (M = Ti, Nb) and dithioacetic acid, CH[sub 3]CS[sub 2]H, is described. Both compounds are characterized by elemental analysis, [sup 1]H and [sup 13]C NMR spectroscopy, infrared spectroscopy, mass spectrometry, and X-ray crystallography. Compound 1 crystallizes in orthorhombic space group Pbca. Compound 1 exists in the crystalline state as discrete seven-coordinate molecules; the coordination environment of the central Ti(IV) atom is a slightly distorted pentagonal bipyramid. A [eta][sup 5]-C[sub 5]H[sub 5] ring occupies one axial site, two bidentate dithioacetate groups occupy four equatorial sites, and a third bidentate dithioacetate group spans the remaining axial and equatorial sites. The average equatorial Ti-S distance of 2.619 [angstrom] is appreciably longer than the axial Ti-S distance, 2.545(3) [angstrom]. Compound 2 crystallizes in space group P2[sub 1]/c. Crystals of 2 consist of discrete seven-coordinate molecules; the coordination environment of the central Nb(V) atom is a severely distorted pentagonal bipyramid. A [eta][sup 5]-C[sub 5]H[sub 5] ring occupies one axial site, and a [open quotes]side-on[close quotes] bonded disulfide, [eta][sup 2]-S[sub 2], occupies two equatorial sites. The remaining positions are occupied by two nonequivalent bidentate dithioacetate ligands. A variable-temperature [sup 1]H NMR study on 2 shows rapid interconversion between the two dithioacetate environments at 47[degrees]C ([Delta]G[double dagger] = 1.7 [+-] 0.1 kcal mol[sup [minus]1]). 46 refs., 1 fig., 7 tabs.
- OSTI ID:
- 5716963
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:13; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CARBON 13
CARBON ISOTOPES
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
EVEN-ODD NUCLEI
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MASS SPECTROSCOPY
MOLECULAR STRUCTURE
NIOBIUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RESONANCE
SCATTERING
SPECTROSCOPY
STABLE ISOTOPES
SULFUR COMPOUNDS
SYNTHESIS
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION
YIELDS