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η4-Coordination of Dienes and Heterodienes to the TripodCobalt(I) Template [CH3C(CH2PPh2)3Co]+: Synthesis, Structure, and Dynamics

✍ Scribed by Rolf Rupp; Axel Frick; Gottfried Huttner; Peter Rutsch; Ute Winterhalter; Annette Barth; Peter Kircher; Laszlo Zsolnai

Publisher
John Wiley and Sons
Year
2000
Tongue
English
Weight
649 KB
Volume
2000
Category
Article
ISSN
1434-1948

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✦ Synopsis

CH 3 C(CH 2 PPh 2 ) 3 CoCl (1) is easily accessible from CH 3 C(CH 2 PPh 2 ) 3 CoCl 2 by reduction with activated zinc powder. Upon dehalogenation with TlPF 6 , 1 reacts with dienes to give [tripodCo I -(η 4 -diene)] + (2). The heterodienes acrolein and methyl vinyl ketone produce the analogous η 4heterodiene compounds 3. When crotonaldehyde is used as the potential η 4 -diene ligand, decarbonylation is observed leading to [tripodCo I -(CO) 2 ] + (4). Reaction of [tripodCo aq ](BF 4 ) 2 with allyl mercaptan produces [tripodCo I -(η 4 -thioacrolein)] + (3a) through dehydrogenation of the ligand precursor. 1,2-Diketones such as benzil and phenanthrenequinone do not coordinate in a η 4 fashion but rather generate η 2 -coordinate enediolato ligands by an electron-transfer process, resulting in compounds of the type {tripodCo III -[η 2 -RC(O)=C(O)R]} + (5). All the compounds have

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