Formation of cation-anion complexes in the photochemical reaction of molybdenocene dihydrode with iron pentacarbonyl. Crystal structures of (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ and (Cp/sub 2/Mo(CO)H)/sup +/(CoMo(CO)/sub 3/)/sup -/ (triclinic modification) (in Russian)
The reaction of Cp/sub 2/MoH/sub 2/ with Fe(CO)/sub 5/ in boiling benzene under UV irradiation gives the ionic complexes (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ (I) and (Cp/sub 2/Mo(CO)H)/sup +/(CpMo(CO)/sub 3/)/sup -/ (II), whose structures were established by x-ray diffraction analysis (Syntex P2/sub 1/ automatic diffractometer, lambda Mo K/sub ..cap alpha../, graphite monochromator, theta/2theta scan technique, full-matrix least-squares method, isotropic variant for I on the basis of 2112 reflections to % = 0.11 and anisotropic variant for II on the basis of 3770 values of hkl to R = 0.052). In complexes I and II the (CpMo(CO)H)/sup +/ fragment is a tapered sandwich with an eclipsed conformation of the rings. In complex I the angle between the rings is 33.9/sup 0/, the mean Mo-C(C/sub 5/H/sub 5/) distance is 2.28(3) A, the mean Mo-C(CO) distance is 2.03(3) A, and the mean Mo-H distance is 1.78(10) A. The corresponding parameters in complex II are: 32.4/sup 0/, 2.296(7), 2.020(6), and 1.87(7) A. The anion in complex I is based on a triangular cluster of Fe atoms, in which one Fe-Fe distance is significantly shorter (2.488(5) A) than the other two (2.702(5) and 2.697(5) A). The Fe atoms forming the short bond are joined additionally by hydride (Fe-H = 2.14 A) and carbonyl (Fe-C = 1.90(3) and 1.93(3) A) Bridges. The remaining groups are terminal. A probable scheme for the process of the formation of complexes I and II has been discussed.
- OSTI ID:
- 6416198
- Journal Information:
- Sov. J. Coordinat. Chem.; (United States), Vol. 11:1; Other Information: Translated from Koordinatsionnaya Khimiya; 11: No. 1, 82-94(Jan 1985)
- Country of Publication:
- United States
- Language:
- Russian
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
CARBONYLS
CRYSTAL MODELS
PHOTOCHEMICAL REACTIONS
IRON COMPLEXES
IRON HYDRIDES
MOLYBDENUM COMPLEXES
MOLYBDENUM HYDRIDES
ANIONS
BOND ANGLE
BOND LENGTHS
CATIONS
CHEMICAL REACTION KINETICS
COMPLEXOMETRY
INTERATOMIC DISTANCES
LATTICE PARAMETERS
LATTICE VIBRATIONS
MONOCLINIC LATTICES
TRICLINIC LATTICES
X-RAY DIFFRACTION
CHARGED PARTICLES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
DIMENSIONS
DISTANCE
HYDRIDES
HYDROGEN COMPOUNDS
IONS
IRON COMPOUNDS
KINETICS
LENGTH
MATHEMATICAL MODELS
MOLYBDENUM COMPOUNDS
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
360602 - Other Materials- Structure & Phase Studies