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À propos de : Intramolecular CH Insertion Reactions of(Pentamethylcyclopentadienyl)Rhenium AlkynylcarbeneComplexes        

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  • Intramolecular CH Insertion Reactions of(Pentamethylcyclopentadienyl)Rhenium AlkynylcarbeneComplexes
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  • Thermolysis of the alkynylcarbene complex Cp*(CO)2ReC(Ph)13C⋮13CTol (5) at 120 °C resulted in rapid equilibration (t1/2 = 33 min) to a 1:1 mixture of 5 and Cp*(CO)2Re13C(Tol)13C⋮CPh (7) via a [1,3]-rhenium shift. Extended thermolysis of the symmetrically substituted alkynylcarbene complex Cp*(CO)2ReC(Ph)C⋮CPh (6) produced the CH insertion product {η5:η2-[C5(CH3)4CH2CH(Ph)C⋮CPh]}Re(CO)2 (10).
  • Thermolysis of the alkynylcarbene complex Cp*(CO)2ReC(Ph)13C⋮13CTol (5) at 120 °Cresulted in rapid equilibration (t1/2 = 33 min) to a 1:1 mixture of 5 and Cp*(CO)2Re13C(Tol)13C⋮CPh (7) via a [1,3]-rhenium shift. Extended thermolysis of this mixture providedthe CH insertion products {η5:η2-[C5(CH3)4CH213CH(Tol)13C⋮CPh]}Re(CO)2 (8) and {η5:η2-[C5(CH3)4CH2CH(Ph)13C⋮13CTol]}Re(CO)2 (9). Thermolysis of the symmetrically substitutedalkynylcarbene complex Cp*(CO)2ReC(Ph)C⋮CPh (6) produced the CH insertion product{η5:η2-[C5(CH3)4CH2CH(Ph)C⋮CPh]}Re(CO)2 (10). The CH insertion of Cp*(CO)2ReC(Ph)C⋮CC6D5 (6-HD) was monitored at low conversion before complete equilibration withCp*(CO)2ReC(C6D5)C⋮CPh (6-DH) occurred. An excess of {η5:η2-[C5(CH3)4CH2CH(C6D5)C⋮CPh]}Re(CO)2 (13-HD) over {η5:η2-[C5(CH3)4CH2CH(Ph)C⋮CC6D5]}Re(CO)2 (13-DH)provides evidence for site-selective CH insertion of the remote alkyne carbon into the CHbond of a Cp* methyl group.
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