
%0 Journal Article
%A Corrigan, PA 
%A Dickson, RS 
%A Fallon, GD 
%A Michel, LJ 
%A Mok, C 
%T Reactions of But-2-yne and Hexafluorobut-2-yne with Dicarbonyl(&#951;-pentamethylcyclopentadienyl)-cobalt, -rhodium and -iridium. Structure of the iridium complex (&#951;-C<sub>5</sub>Me<sub>5</sub>)Ir<sub>2</sub>(CO)<sub>2</sub>(CF<sub>3</sub>C<sub>2</sub>CF<sub>3</sub>)<sub>3</sub>H
%J Australian Journal of Chemistry
%D 1978/09/01
%V 31
%N 9
%P 1937-1951
%K 
%R https://doi.org/10.1071/CH9781937
%U https://www.publish.csiro.au/paper/CH9781937 
%X The reactions of but-2-yne and hexafluorobut-2-yne with the complexes (&#951;-C5Me5)M(CO)2, M = CO, Rh, or Ir, have been compared. A cyclopentadienone complex, (&#951;-C5Me5)M[C4Me4CO]2 is the major product formed in the reaction of but-2-yne with (&#951;-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 (&#951;-C5Me5)M[C4(CF3)4CO], M = CO and Rh, were major products from the reactions of hexa- fluorobut-2-yne with (&#951;-C5Me5)M(CO)2. Hexakis(trifluoromethyl)benzene and the tetrahapto- benzene complexes (&#951;-C5Me5)M[&#951;4-C6(CF3)6], M = Co or Rh, were minor products from these reactions. Small amounts of the dirhodium complexes (&#951;-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 (&#951;-C5Me5)Ir(CO)2 and but-2-yne, but the reaction with hexafluorobut-2-yne gives two organoiridium complexes. One complex, (&#951;-C5Me5)Ir(CO)2(CF3C2CF3), incorporates an iridiocyclobutenone ring and one terminal carbonyl. The second, (&#951;-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) &#506;. 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 &#963;-bonded C(CF3)=C(CF3)H group, and the other iridium atom [Ir-Ir distance 2.737(1) &#506;]. 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. 
