Phosphorus-bridged ansa-metallocene complexes of titanium, zirconium, and hafnium: The syntheses and structures of [PhP(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} and [Ph(E)P(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} (E = O, S, Se) derivatives

Journal Article · Mon Jan 04 04:00:00 EST 1999 · Organometallics

DOI:https://doi.org/10.1021/om9807396· OSTI ID:315987

Shin, J H; Hascall, T; Parkin, G ^[1]

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1. Columbia Univ., New York, NY (United States). Dept. of Chemistry

A series of phosphorus-bridged ansa-metallocene complexes of titanium, zirconium, and hafnium, [PhP(XC{sub 5}Me{sub 4}){sub 2}]MX{sub 2} and [Ph(E)P(C{sub 5}Me{sub 4}){sub 2}]MX{sub 2} (X = Cl, Me, CO, (Se{sub 3}){sub 0.5}; E = O, S, Se), has been synthesized. Structural characterization by X-ray diffraction indicates that, in comparison to their non-ansa counterparts (C{sub 5}Me{sub 5}){sub 2}MX{sub 2}, the cyclopentadienyl groups in phosphorus-bridged complexes are displaced from symmetric {eta}{sup 5}-coordination toward {eta}{sup 3}-coordination. Such {eta}{sup 3},{eta}{sup 3}-coordination creates more electrophilic metal centers than those in their permethylcyclopentadienyl counterparts, as judged by the {nu}(CO) stretching frequencies of the zirconium dicarbonyl complexes Cp{sup *}{sub 2}Zr(CO){sub 2} (1946 and 1853 cm{sup {minus}1}) and [PhP(C{sub 5}Me{sub 4}){sub 2}]Zr(CO){sub 2} (1959 and 1874 cm{sup {minus}1}).

• Sponsoring Organization: USDOE, Washington, DC (United States)
• DOE Contract Number: FG02-93ER14339
• OSTI ID: 315987
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 1 Vol. 18; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
COORDINATION VALENCES
HAFNIUM COMPLEXES
MOLECULAR STRUCTURE
PHOSPHORUS COMPLEXES
SYNTHESIS
TITANIUM COMPLEXES
X-RAY DIFFRACTION
ZIRCONIUM COMPLEXES