Reactions of Ruthenium Acetylide Complexes with Isothiocyanate
Resource
Organometallics 17 (12): 2534-2542
Journal
Organometallics
Journal Volume
17
Journal Issue
12
Pages
2534-2542
Date Issued
1998
Date
1998
Author(s)
Abstract
Treatment of Cp(PPh3)[P(OMe)3]RuC⋮CPh (2; Cp = η5-C5H5) with PhNCS at room temperature affords the [2 + 2] cycloaddition (3a), containing a four-membered ring, and the neutral vinylidene phosphonate complex Cp(PPh3)[P(O)(OMe)2]RuCC(Ph)C(SH)NPh (4a) in a 9:1 ratio. Formation of 4a results from an Arbuzov-like dealkylation reaction possibly after addition of PhNCS. The same reaction at 40 °C affords a higher yield of 4a (5a; R = Ph) which results from addition of a second isothiocyanate to the four-membered ring of 3a. The reaction of 2 with PhCH2NCS at room temperature directly affords the six-membered-ring product 5b (R = CH2Ph). Trimerization of phenyl isothiocyanate is catalyzed by Cp(dppe)RuC⋮CPh (1‘; dppe = Ph2PCH2CH2PPh2) in refluxing CH2Cl2. This catalytic reaction proceeds through a pathway in which the first two steps are the same as those observed in the reaction of 2a. An attempt to purify the precursor of the trimerization product gave the cocrystallization of 1‘ and (PhNCS)3 (8). The structures of 3a, 4a, 5b, and the cocrystallization product of 1‘ and 8 have been determined by single-crystal X-ray diffraction analysis.
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