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Article << Previous     |     Next >>   Contents Vol 31(9)

Reactions of But-2-yne and Hexafluorobut-2-yne with Dicarbonyl(η-pentamethylcyclopentadienyl)-cobalt, -rhodium and -iridium. Structure of the iridium complex (η-C5Me5)Ir2(CO)2(CF3C2CF3)3H

PA Corrigan, RS Dickson, GD Fallon, LJ Michel and C Mok

Australian Journal of Chemistry 31(9) 1937 - 1951
Published: 1978


The reactions of but-2-yne and hexafluorobut-2-yne with the complexes (η-C5Me5)M(CO)2, M = CO, Rh, or Ir, have been compared. A cyclopentadienone complex, (η-C5Me5)M[C4Me4CO]2 is the major product formed in the reaction of but-2-yne with (η-C5Me5)M(CO)2, M = Co or Rh. The cobalt system also gives some hexamethylbenzene whereas the rhodium system yields the pentadienone-dirhodium complex (q-C5Me5)2Rh2(MeC2Me)2CO. The cyclopentadienone complexes (η-C5Me5)M[C4(CF3)4CO], M = CO and Rh, were major products from the reactions of hexa- fluorobut-2-yne with (η-C5Me5)M(CO)2. Hexakis(trifluoromethyl)benzene and the tetrahapto- benzene complexes (η-C5Me5)M[η4-C6(CF3)6], M = Co or Rh, were minor products from these reactions. Small amounts of the dirhodium complexes (η-C5Me5)2Rh2(CF3C2CF3)2(CO)n, n = 1 or 2, were also isolated from the rhodium system under some reaction conditions.

No products could be isolated from the reaction between (η-C5Me5)Ir(CO)2 and but-2-yne, but the reaction with hexafluorobut-2-yne gives two organoiridium complexes. One complex, (η-C5Me5)Ir(CO)2(CF3C2CF3), incorporates an iridiocyclobutenone ring and one terminal carbonyl. The second, (η-Ir5Me5)Ir2(CO)2(CF3C2CF3)3H, has been characterized crystallographically. The compound crystallizes with four molecules in the orthorhombic space group Pnma in a cell of di- mensions a 14.262(5), b 13.293(5), c 15.027(5) Ǻ. The structure has been refined by standard methods to a conventional R factor of 0.072, based on 2061 reflections above background. The environments of the two iridium atoms are markedly different. One forms part of a metallopentadiene ring, and it is also attached to two terminal carbonyls, a σ-bonded C(CF3)=C(CF3)H group, and the other iridium atom [Ir-Ir distance 2.737(1) Ǻ]. Overall, this iridium has a distorted octahedral geometry. The second iridium is n-bonded in a conventional sandwich manner to the C5Me5 and iridiocycle rings; these two rings have a staggered conformation and are close to parallel.

Full text doi:10.1071/CH9781937

© CSIRO 1978

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