CSIRO Publishing blank image blank image blank image blank imageBooksblank image blank image blank image blank imageJournalsblank image blank image blank image blank imageAbout Usblank image blank image blank image blank imageShopping Cartblank image blank image blank image You are here: Journals > Australian Journal of Chemistry   
Australian Journal of Chemistry
Journal Banner
  An international journal for chemical science
 
blank image Search
 
blank image blank image
blank image
 
  Advanced Search
   

Journal Home
About the Journal
Editorial Structure
Contacts
For Advertisers
Content
Online Early
Current Issue
Just Accepted
All Issues
Virtual Issues
Special Issues
Research Fronts
Sample Issue
Covers
For Authors
General Information
Scope
Submit Article
Author Instructions
Open Access
For Referees
Referee Guidelines
Review an Article
For Subscribers
Subscription Prices
Customer Service
Print Publication Dates

blue arrow e-Alerts
blank image
Subscribe to our Email Alert or RSS feeds for the latest journal papers.

red arrow Connect with us
blank image
facebook twitter LinkedIn

Affiliated with RACI

Royal Australian Chemical Institute
Royal Australian
Chemical Institute


 

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

Abstract

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

blank image
Subscriber Login
Username:
Password:  

 
PDF (1006 KB) $25
 Export Citation
 Print
  


    
Legal & Privacy | Contact Us | Help

CSIRO

© CSIRO 1996-2015