ISSN:
0947-6539
Keywords:
Arbuzov reactions
;
biphenylene
;
cyclohexadienyl complexes
;
manganese
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Biphenylene readily coordinates through one of the phenyl rings to form [(η6-biphenylene)Mn(CO)3]+ (2+), the X-ray structure of which is reported. The nucleophiles H-, Me-, Me3CC(O)CH-2 and P(OEt)3 add to 2+ at a bridgehead carbon to afford high yields of cyclohexadienyl complexes (3); the X-ray structure of the product of hydride addition is reported. P(OMe)3 adds to 2+ to give 3, which then undergoes a spontaneous Arbuzov elimination to the dimethyl phosphonate adduct. Nucleophilic additions to 2+ are unusual in that they occur at a substituted (bridgehead) carbon. A kinetic and thermodynamic study of the reaction with P(OEt)3 shows that the bridgehead carbons in 2+ are orders of magnitude more electrophilic than are the arene carbons in unstrained [(arene)Mn(CO)3]+ systems.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970030113
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