Mono(pentamethylcyclopentadienyl)thorium chemistry. Formation and structural characterization of a novel triflate-bridged dimeric thorium complex

Journal Article · Thu Jun 01 04:00:00 EDT 1995 · Organometallics

DOI:https://doi.org/10.1021/om00006a028· OSTI ID:70370

Butcher, R J; Clark, D L; Grumbine, S K; Watkin, J G ^[1]

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1. Los Alamos National Lab., NM (United States)

We have shown that the reaction of an actinide amide complex, such as Th[N(SiMe{sub 3}){sub 2}]{sub 3}(OTf) (2), with Cp{sup *}H can provide an alternative to the traditional halide metathesis routes to mono(pentamethylcyclopentadienyl)actinide species. As reported recently for the Group IV metals, this synthetic method can offer distinct advantages over halide metathesis procedures, most notably by eliminating the problem of salt retention by the actinide product. The X-ray crystal structure of the dinuclear actinide complex Cp{sup *}[(Me{sub 3}Si){sub 2}N]Th({mu}{sub 2}-OSO{sub 2}CF{sub 3}) [N(SiMe{sub 3})(SiMe{sub 2}CH{sub 2})]Cp{sup *} (4), formed from reaction of 2 with Cp{sup *}H, has been determined and reveals an unusual molecular geometry in which three {eta}{sup 2}-triflate ligands bridge the two thorium metal centers. We have proposed a mechanism to explain the formation of 4 and have shown that several of the proposed mechanistic steps may be verified in independent reactions. Further studies of the reactivity and catalytic properties of mono-Cp{sup *} thorium complexes with alkoxide and alkyl supporting ligands are currently underway. 17 refs., 1 fig., 3 tabs.

• Sponsoring Organization: USDOE
• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 70370
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 6 Vol. 14; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
BOND ANGLE
BOND LENGTHS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CRYSTALLOGRAPHY
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
NMR SPECTRA
NUMERICAL DATA
ORGANOMETALLIC COMPOUNDS
STRUCTURAL CHEMICAL ANALYSIS
THORIUM COMPLEXES
TOLUENE
X-RAY DIFFRACTION