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Regioselective addition of tert-BuN C to the alpha carbon atom of the allenyl ligand in [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(2)(alpha,beta)-(H)C-alpha=C-beta=C gamma H2}]: Formation of [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(1)-(tert-BuN C)C=CCH3}] and [Fe-2(CO)(6)(mu-PPh2)(mu-eta(1):eta(2)-{tert-BuNHC(O)CH2}C=CH2)] via competitive 1,3-hydrogen migration and hydrolysis of the reactive allene-bridged intermediate [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(1)-(tert-BuNC)HC=C=CH2}]

Lookup NU author(s): Dr Simon Doherty, Mark Waugh, Thomas Scanlan, Emeritus Professor Bill Clegg, Dr Mark Elsegood


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Addition of tert-BuN=C to the sigma-eta-allenyl complex [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(alpha,beta)(2)-(H)-C-alpha=C-beta=CgammaH2}] results in nucleophilic addition to C-alpha to give the mu-eta(1):eta(1)-parallel to-alkyne [Fe-2(CO)(6)-(mu-PPh2){mu-eta(1):eta(1)-(tert-BuN=C)C=CCH3}] (2) and the beta,gamma-unsaturated amide [Fe-2(CO)(6)(mu-PPh2)(mu-eta(1):eta(2)-{tert-BuNHC(O)CH2}C=CH2)] (3). Compounds 2 and 3 are proposed to form via initial nucleophilic attack at C-alpha to give [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(1)-(tert-BuNC)HC=C=CH2}], an unstable zwitterionic allene-bridged intermediate which subsequently undergoes either a 1,3-hydrogen migration to give 2 or hydrolysis by extraneous water to give the beta,gamma-unsaturated amide 3. An alternative pathway involving initial nucleophilic attack at C-beta to give the metallacyclopentene intermediate [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(1)-HC=C(tert-BuNC)CH2}], followed by 1,3-hydrogen migration and C-beta to C-alpha tert-BuN=C migration has been considered. Isotope labeling experiments using [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(alpha,beta)(2)-(D)-C-alpha=C-beta=CgammaH2}] (1-d(1)) are consistent with a large primary kinetic isotope effect for the transfer of hydrogen between C-alpha and C-gamma. Addition of excess isopropylamine to a hexane solution of 2 gave the amidinium-substituted mu-eta(1):eta(1)-parallel alkyne derivative [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(1)-C(tert-BuHNC)(NHPri)C=CCH3}] (4), in near quantitative yield via addition of N-H across the C-N multiple bond. Chloroform solutions of 3 smoothly decarbonylate over several days to afford [Fe-2(CO)(5)(mu-PPh2)(mu-eta(1)(C):eta(1)(O):eta(2)(C)-{tert-BuNHC(O)CH2}C=CH2)] (5), which contains a five-membered metallacycle by virtue of coordination of the amide carbonyl oxygen atom. The single-crystal X-ray structures of 2, 4, and 5 are reported.

Publication metadata

Author(s): Doherty S, Hogarth G, Waugh M, Scanlan TH, Clegg W, Elsegood MRJ

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 1999

Volume: 18

Issue: 16

Pages: 3178-3186

Print publication date: 10/07/1999

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society


DOI: 10.1021/om9901630


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