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A comparison between CpCo-stabilized cyclopentadienone complexes and their O-alkylated or protonated congeners

The CpCo-stabilized tricyclic cyclopentadienone complexes 4 and 6 as well as the cyclopentadienonophane 8 were treated with an excess of triethyloxonium tetrafluoroborate. This yields, in case of 4 and 6, to the yellow colored O-ethylcobalticinium salts 5 and 7. In the case of 8 the alkylation yield...

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Main Authors: Gleiter, Rolf (Author) , Roers, Rolf (Author) , Rominger, Frank (Author) , Nuber, Bernhard (Author) , Hyla-Kryspin, Isabella (Author)
Format: Article (Journal)
Language:English
Published: 29 November 2000
In: Journal of organometallic chemistry
Year: 2000, Volume: 610, Issue: 1/2, Pages: 80-87
ISSN:1872-8561
DOI:10.1016/S0022-328X(00)00431-9
Online Access:Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1016/S0022-328X(00)00431-9
Verlag, lizenzpflichtig, Volltext: http://www.sciencedirect.com/science/article/pii/S0022328X00004319
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Author Notes:Rolf Gleiter, Rolf Roers, Frank Rominger, Bernhard Nuber, Isabella Hyla-Kryspin

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520 |a The CpCo-stabilized tricyclic cyclopentadienone complexes 4 and 6 as well as the cyclopentadienonophane 8 were treated with an excess of triethyloxonium tetrafluoroborate. This yields, in case of 4 and 6, to the yellow colored O-ethylcobalticinium salts 5 and 7. In the case of 8 the alkylation yielded the mono- and bis-O-ethylcobalticinium salts 9 and 10, respectively. Protonation of the superphane 8 yields to the diprotonated superphane 11. X-ray investigations allowed a comparison of 5 and 11 with 4 and 8. This comparison shows that the CpCo units in 4 and 8 are more tightly bound to the butadiene units of the cyclopentadienone rings than to the CO groups. In the case of 5 and 11 the distances to all five carbons of the alkoxycyclopentadienyl units are approximately equal. This difference in the bonding was substantiated by model calculations on (η5-cyclopentadienone)(η5-cyclopentadienyl)cobalt (2) and its O-protonated form 12 as well as (η4-butadiene)(η5-cyclopentadienyl)cobalt (13) and the cobalticinium ion (14). The results show similarities between 2 and 13 as well as 12 and 14. 
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