Addition of methyl triflate to a hafnocene dinitrogen complex: stepwise n(2) methylation and conversion to a hafnocene hydrazonato compound.
Treatment of the hafnocene complex bearing a strongly activated, side-on bound dinitrogen ligand, [(eta(5)-C(5)Me(4)H)(2)Hf](2)(mu(2),eta(2),eta(2)-N(2)), with two equivalents of methyl triflate yielded a mixture of products, one of which was identified as the triflato hafnocene methyl diazenide compound, (eta(5)-C(5)Me(4)H)(2)Hf(OTf)(N(2)(CH(3))), arising from methylation of one of the nitrogen atoms. This reactivity contrasts with that of the zirconocene congener, [(eta(5)-C(5)Me(4)H)(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)), where methyl triflate addition yields a variety of products that lack new nitrogen-carbon bonds. The methylated hafnocene product, (eta(5)-C(5)Me(4)H)(2)Hf(OTf)(N(2)(CH(3))) provides a platform for additional transformations for the functionalized dinitrogen core. Treatment with additional methyl triflate results in a second nitrogen-carbon bond formation to yield a rare example of a triflato hafnocene hydrazonato complex. Loss of methane and formation of the hafnocene bis(triflate) accompany the transformation. Isotopic labeling studies and other experiments are consistent with a pathway involving initial methylation of the unsubstituted nitrogen in the methyl diazenido ligand followed by deprotonation by a triflate anion.
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, USA.
Donald J
DJ
Knobloch
David
D
Benito-Garagorri
Wesley H
WH
Bernskoetter
Ivan
I
Keresztes
Emil
E
Lobkovsky
Hannah
H
Toomey
Paul J
PJ
Chirik