Reactivity of the cyanometalate Na[Cp[prime]Mn(CO)[sub 2]CN] with titanium, zirconium, and hafnium halides. Crystal and molecular structure of the [mu]-cyano [mu]-oxo tetranuclear complex [Cp[sub 2]Zr([mu]-NC)MnCp[prime]-(CO)[sub 2]][sub 2]([mu]-O) (Cp = [eta]-C[sub 5]H[sub 5]; Cp[prime] = [eta]-MeC[sub 5]H[sub 4])
- Universite Louis Pasteur, Cedex (France)
- Universite Louis Pasteur, Cedex (France) Universita di Parma (Italy)
- Universita di Parma (Italy)
In contrast to most carbonylmetalates of the transition metals, cyanide-substituted anionic complexes such as Na[Cp[prime]Mn-(CO)[sub 2]CN] (Cp[prime] = [eta]-MeC[sub 5]H[sub 4]) do not exhibit a metal-centered HOMO. Instead, this orbitals is essentially nitrogen-based, which favors coordination to metal centers through the cyanide moiety, thus generating Mn-CN-M[prime] chain systems. The cyanometalate ligand [Cp[prime]Mn(CO)[sub 2]CN][sup [minus]] has been observed to coordinate via the CN[sup [minus]] in both terminal and bridging modes. More complex interactions can also be generated, notably in the octanuclear Pd[sub 4]Mn[sub 4] cluster [(OC)Pd([mu]-NC)MnCp[prime](CO)[sub 2]][sub 4], whose novel molecular architecture is characterized by an orthogonal arrangement of helical units. This cluster was formed quantitatively by the reaction of [Cp[prime]Mn(CO)[sub 2]CN][sup [minus]] with [Pd[sub 4]([mu]-CO)[sub 4]([mu]-OAc)[sub 4]], and a diversity of palladium-cyanometalate interactions are generated which maintain the tetrameric Pd structure: a direct Mn-Pd bond and semibridging manganese-bound CO and CN ligands, as well as Mn-([mu]-CN)-Pd bridges. In order to further study the bonding capabilities of Na[Cp[prime]Mn-(CO)[sub 2]CN], we have examined its reactivity with the titanocene, zirconcene, and hafnocene dichlorides, as well as with related titanium(III) and -(IV) precursors.
- OSTI ID:
- 5646558
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 32:15; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HAFNIUM CHLORIDES
CHEMICAL REACTIONS
HAFNIUM COMPLEXES
MANGANESE COMPLEXES
MOLECULAR STRUCTURE
TITANIUM CHLORIDES
TITANIUM COMPLEXES
ZIRCONIUM COMPLEXES
ZIRCONIUM COMPOUNDS
BONDING
CARBONYLS
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
CYANIDES
ORGANOMETALLIC COMPOUNDS
X-RAY DIFFRACTION
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
FABRICATION
HAFNIUM COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
JOINING
ORGANIC COMPOUNDS
REFRACTORY METAL COMPOUNDS
SCATTERING
SYNTHESIS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties