Catalytic carbon-carbon bond activation and functionalization by nickel complexes

Journal Article · Mon Sep 27 04:00:00 EDT 1999 · Organometallics

DOI:https://doi.org/10.1021/om990387i· OSTI ID:20013594

Edelback, B L; Lachicotte, R J; Jones, W D

The nickel alkyne complexes (dippe)Ni(PhC{triple{underscore}bond}CPh), 2, (dippe) Ni(MeO{sub 2}CC{triple{underscore}bond}CCO{sub 2}Me), 3, (dippe)Ni(CH{sub 3}OCH{sub 2}C{triple{underscore}bond}CCH{sub 2}OCH{sub 3}), 4, and (dippe)Ni(CF{sub 3}C{triple{underscore}bond}CCF{sub 3}), 5, were synthesized (dippe = bis(diisopropylphosphino)ethane) and characterized by {sup 1}H, {sup 31}P, and {sup 13}C{l{underscore}brace}{sup 1}H{r{underscore}brace} NMR spectroscopy. Complexes 1, 2, and 3 were characterized by X-ray crystallography. The thermolysis of complex 1 or 2 (120 C) in the presence of excess biphenylene and excess alkyne results in very slow catalytic formation of the corresponding 9,10-disubstituted phenanthrene. However, addition of {approximately}6 mol % O{sub 2} (based on the metal complex) to the reaction mixture results in an acceleration in catalysis at lower temperatures ({approximately}70--80 C). The thermolysis of complexes 3 or 4 with excess biphenylene and excess alkyne leads to the alkyne cyclotrimerization product as the major organic species formed in the reaction. Fluorenone was catalytically produced by heating (dippe)Ni(CO){sub 2}, biphenylene, and CO. Catalytic insertion of 2,6-xylylisocyanide into the strained C-C bond of biphenylene was also achieved by heating (dippe)Ni(2,6-xylylisocyanide){sub 2}, excess biphenylene, and 2,6-xylylisocyanide. Mechanistic schemes are proposed for these reactions.

• Research Organization: Univ. of Rochester, NY (US)
• Sponsoring Organization: US Department of Energy
• DOE Contract Number: FG02-86ER13569
• OSTI ID: 20013594
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 20 Vol. 18; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ALKYNES
BINDING ENERGY
CATALYSIS
NICKEL COMPLEXES
REACTION KINETICS