Carbon dioxide chemistry. Synthesis, properties, and structural characterization of the stable bis(carbon dioxide) adducts of molybdenum
The bis(carbon dioxide) adduct, trans-Mo(CO/sub 2/)/sub 2/(PMe/sub 3/)/sub 4/, 1, has been prepared from the reaction of cis-Mo(N/sub 2/)/sub 2/(PMe/sub 3/)/sub 4/ with CO/sub 2/ under pressure (4-5 atm). The interaction of 1 with several small molecules has been studied. In particular, reaction with COS affords a seven-coordinate S,S'-dithiocarbonate, Mo(S/sub 2/CO)(CO)/sub 2/(PMe/sub 3/)/sub 3/, 2, while interaction with various isocyanides yields the new carbon dioxide complexes trans,mer-Mo(CO/sub 2/)/sub 2/(CNR)(PMe/sub 3/)/sub 3/, 3 (R = Me, 3a; i-Pr, 3b; t-Bu, 3c; Cy, 3d; CH/sub 2/C/sub 6/H/sub 5/, 3e). The new compounds have been characterized by analytical and spectroscopic (IR and /sup 1/H, /sup 13/C, and /sup 31/P NMR) studies. The molecular structures of 2, 3b, and 3e have been determined by x-ray crystallography. Compound 2 is orthorhombic and belongs to the space group Pna2/sub 1/ with a = 14.003 (2) A, b = 9.767 (2) A, c = 15.127 (2) A, D/sub c/ = 1.52 g cm/sup -3/, and Z = 4. 3b crystallizes in the monoclinic space group C2/c with unit cell parameters a = 24.47 (3) A, b = 13.01 (1) A, c = 16.77 (1) A, ..beta.. = 132.41 (3)/sup 0/, and D/sub c/ = 1.35 g cm/sup -3/ for Z = 8. Crystals of 3e are monoclinic, space group P2/sub 1//c with a = 11.563 (8) A, b = 11.792 (7) A, c = 18.57 (1) A, ..beta.. = 90.42 (4)/sup 0/, D/sub c/ = 1.39 g cm/sup -3/, and Z = 4. 3b and 3e are isostructural, with the Mo atom bonded to two trans, staggered CO/sub 2/ molecules, the overall molecular geometry being approximately octahedral.
- Research Organization:
- Universidad de Sevilla, Spain
- OSTI ID:
- 5583952
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:9; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Tantalum(I) alkyne complexes: Ta(CO)/sub 2/(eta/sup 2/-RC=CR)(I)L/sub 2/
Facile interconversions of alkyne and vinylidene ligands on divalent molybdenum and tungsten
Related Subjects
400201* -- Chemical & Physicochemical Properties
ADDUCTS
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
LATTICE PARAMETERS
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
RESONANCE
SCATTERING
SPACE GROUPS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION