Travis N. Valadez, J. Norton, Michelle C. Neary
Sep 14, 2016
Citations
0
Influential Citations
12
Citations
Journal
Organometallics
Abstract
We have investigated the reaction of isonitriles with a permethylzirconocene complex of 2,3-dimethylbutadiene. Cp*2Zr(2,3-dimethylbutadiene) (1) reacts with tert-alkyl isonitriles to give η2-iminoacyl complexes Cp*2Zr[CH2C(CH3)C(CH3)CH2C(NR)] 2 (R = tBu) and 3 (R = 1-adamantyl). Treatment of 2 with excess isopropyl isonitrile gives the η1,η2-bis(iminoacyl) complex Cp*2Zr[C(NiPr)CH2C(CH3)C(CH3)CH2C((NiPr)] (4) and free tert-butyl isonitrile. The reaction of 1 with 2 equiv of isopropyl isonitrile also affords 4, through the intermediate Cp*2Zr[CH2C(CH3)C(CH3)CH2C(NiPr)] (5). Carbonylation of 2 affords the Zr formimidoyl cyclopentadienolate 6. Treatment of a Zr hydride cyclopentadienolate (7), obtained from the carbonylation of 1, with tert-butyl isonitrile also affords 6. Isotopic labeling shows that the insertion of tert-butyl isonitrile into 1 and 7 is reversible. All complexes were characterized by spectroscopic and crystallographic methods.