1. Towards the Synthesis and Characterization of Copper(I)-Arene Compounds Using Phenyl- and Naphthyl-Appended NS2-Macrocyclic Ligands
Thora R. Maltais.; Cedric P. Owens; Michelle S. Kim; Paul J. Lee; and Rebecca R. Conry*
*Department of Chemistry, Colby College, Waterville, ME, USA
Although many transition-metal π-arene complexes have been reported, Cu(I)-arene complexes are still relatively rare. The Conry group previously reported the Cu(I)-arene complex 1 containing a ligand with a pendant 1-naphthylene group bound to Cu(I). The arene interaction was shown to occur both in the solid and solution states.2,4 We are expanding these studies by synthesizing additional Cu(I)-arene complexes. These complexes and similar non-arene complexes made to interpret spectra feature pendant phenyl and 1-naphthyl groups to probe Cu(I)-arene binding strengths and locations.
Ligand Synthesis
Ligands were formed from the addition of a phenyl or naphthyl group to the NS2-macrocyclic ring.2,3
Introduction 2 L1
37%
L14 was synthesized in one step. 1 3
L2’
42% L2
77%
L2 was synthesized in three steps. The first step, the formation of 3, is not shown.5
Compound Synthesis
Four complexes are made from [Cu(CH3CN)4]PF66 and L1 and L2 in the presence of PPh3 or additional CH3CN.4
Results
Both ligands have been successfully synthesized and characterized by NMR spectroscopy. Complexes C1 and C2 have been successfully synthesized and characterized via NMR, UV-vis, ESI, and IR spectroscopy.
and C1
66% C2
33%
Future Directions
and C3
51% C4
We are currently synthesizing and characterizing C3 and C4. The next phase includes the synthesis and characterization of the two Cu(I)-arene complexes (C5 and C6).
To avoid strongly binding additional ligands, L1 and L2, will be reacted with (C6H6)[CuOTf]27 to try to form Cu(I)-arene complexes.4
and
Tf =
1. Conry, R. R. et al. Organometallics. 2004, 23,
2. Conry, R. R. Striejewske, W. S. Organometallics, 1998, 17,
3. Chandrasekhar, S.; McAuley, A. Inorg. Chem. 1992, 31,
4. Unpublished synthesis based on: Conry R. R.; Striejewske, W. S.; Tipton A. A.
Inorg. Chem. 1999, 38,
5. Sheehan, J. C.; Chapman, D. W.; Roth R. W. J. Am. Chem. Soc. 1952, 74,
6. Kubas, G. J. Inorg. Synth. 1979, 19,
7. Salomon, R. G.; Kochi, J. K. J. Am. Chem. Soc. 1973, 95,
References C5 C6
Acknowledgements
Colby College and ACS-PRF for funding and A. Alex Tipton for previous results