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])

Journal Article · Wed Jul 21 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00067a031· OSTI ID:5646558

Braunstein, P ^[1]; Cauzzi, D ^[2]; Kelly, D ^[1]; Lanfranchi, M; Tiripicchio, A ^[3]

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1. Universite Louis Pasteur, Cedex (France)
2. Universite Louis Pasteur, Cedex (France) Universita di Parma (Italy)
3. 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), Journal Name: Inorganic Chemistry; (United States) Vol. 32:15; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BONDING
CARBONYLS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
CYANIDES
DIFFRACTION
FABRICATION
HAFNIUM CHLORIDES
HAFNIUM COMPLEXES
HAFNIUM COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
JOINING
MANGANESE COMPLEXES
MOLECULAR STRUCTURE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REFRACTORY METAL COMPOUNDS
SCATTERING
SYNTHESIS
TITANIUM CHLORIDES
TITANIUM COMPLEXES
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
ZIRCONIUM COMPLEXES
ZIRCONIUM COMPOUNDS