ISSN:
0009-2940
Keywords:
Cycloalkene ligands
;
Cyclopentylidene ligands
;
Deprotonotion reactions
;
Rhenium complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reactions of [(η5-C5H5)Re(NO)(PPh3)(ClC6H5)]+BF-4 and (n = 5, a; 6, b; 7, c; 8, d) give cycloalkene complexes (6a - d, 94 to 79%). A crystal structure of the methylcyclopentadienyl analog of 6a shows the Re - plane and Re - PPh3 bond to be coplanar, with the vinyl protons syn to the cyclopentadienyl ligand. Reaction of 6a and tBuO-K+ leads to the vinyl complex (9a, 90%) instead of expected allyl complex (10a) Analogous reactions of 6b - d give varying mixtures of 9b - d/10b - d. HBF4 · OEt2 and 9a react to form the cyclopentylidene complex (10+ BF-4, 96%), the stability of which precludes any intermediacy in the deprotonation of 6a. A crystal structure of 11+ PF-6 shows the Re=C—C planes to be perpendicular to the Re - P bond. Spectroscopic features of compounds 6 are analyzed in detail, and NMR data show a high barrier to cyclopentylidene ligand rotation in 11+ BF-4 (ΔG≢ (110°C) ≥ 19 kcal/mol).
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240410
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