Journal article
Solution and solid-state structures of the monomeric, piano-stool mono(peralkylcyclopentadienyl)vanadium(IV) trihalides
Inorganic chemistry, Vol.29(9), pp.1780-1782
05/01/1990
DOI: 10.1021/ic00334a038
Abstract
Low-valent organovanadium chemistry is dominated by the study of mono- and bis(cyclopentadienyl)vanadium compounds.2,3Less studied are compounds with ring alkylation, a derivatization that has been shown to yield reactive compounds such as the highly oxidizing (?-C5H4Me)VCl34Cyclopentadienyl ringperalkylation has been shown to inhibit (though not completely prevent) intramolecular ring metalation in early-transition-metal chemistry. In our research in low-valent mono(peralkylcyclopentadienyl) group 5 chemistry, we were interested in preparing organodi;-vanadium(III) analogues5of (?-C5Me4R)2Ta2X46(R = Me, Et; X = Cl, Br) via reductive dimerization in order to examine comparative structure and reactivity 7between first- and third-row congeners and to develop early-metal-early-metal bonded orga-nodimetallic8chemistry. For such studies, a mono(peralkyl-cyclopentadienyl)vanadium(IV) halide precursor was needed to avoid possible C5H5or C5H4Me metalation during reduction; this compound was expected to possess a three-legged piano-stool structure4rather than the nonbonded structure of the organoditantalum(IV) compounds (?-C5Me4R)2Ta2(µ-X)2X4.9 Previous preparations of mono(cyclopentadienyl)vanadium(IV) halides involved halogenation of CpV(CO)4with X210or SOCl211or of Cp2VCI2with S0CI2.The earliest report of a peralkylcyclopentadienyl derivative halide was that of Bottomley et al.,12 who prepared (C5Me5)VCl3 in very low (unstated) yield from (C5Me5)2VCl2 and SOCI2. Herberhold and co-workers recently reported the high-yield preparation of (C5Me5)VX3 (X = Cl, Br,I) by direct halogenation of (C5Me5)V(CO)4,13 a synthesis that is reproducible in our hands and applicable to the preparation of the C5Me4Et analogues. In this note, we report spectroscopic and spectrometric data for the C5Me5 and C5Me4Et compounds and the solid-state molecular structure of (p-C5Me4Et)VCl3. © 1990, American Chemical Society. All rights reserved.
Details
- Title: Subtitle
- Solution and solid-state structures of the monomeric, piano-stool mono(peralkylcyclopentadienyl)vanadium(IV) trihalides
- Creators
- Michael S HammerLouis Messerle
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.29(9), pp.1780-1782
- Publisher
- American Chemical Society
- DOI
- 10.1021/ic00334a038
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Language
- English
- Date published
- 05/01/1990
- Academic Unit
- Radiology; Chemistry
- Record Identifier
- 9984216586302771
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