Doherty, S and Hogarth, G and Waugh, M and Clegg, W and Elsegood, MRJ (2000) Reactions of alkynes with [Fe<sub>2</sub>(CO)<sub>6</sub>(μ-PPh<sub>2</sub>){μ-η<sup>1</sup>:η<sup>2</sup><sub>αβ</sub>(H)C<sub>α</sub>=C<sub>β</sub>=C<sub>γ</sub>H<sub>2</sub>}]: Formation of diphenylvinylphosphine-functionalized vinyl carbenes via carbon-carbon and carbon-phosphorus bond formation and hydrogen migration. Organometallics , 19 (22) 4557 - 4562.
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Abstract
Reaction of [Fe-2(CO)(6)(mu-PPh2){mu-eta(1):eta(alpha,beta- )(2)(H)C-alpha=C-beta=CgammaH2}] (1) with PhC=CPh results in allenyl-alkyne-phosphido coupling to give [Fe-2(CO)(6)(mu- PPh2){mu-eta(1)(P):eta(3)(C):eta(1)(C)- C(Ph)C(Ph)C(H)C(=CH2)PPh2}] (2), bridged by a diphenylvinylphosphine-substituted vinyl carbene. Under similar conditions 1 reacts with PhC=CMe to give an equal mixture of the two possible regioisomers, [Fe-2(CO)(6)(mu-PPh2){mu- eta(1)(P):eta(3)(C):eta(1)(C)-C(Ph)C(Me)C(H)C(=CH2)PPH2}] (3a) and [Fe-2(CO)(6)(mu-PPh2){mu-eta(1)(P):eta(3)(C):eta(1)(C)- C(Me)C(Ph)C(H)C(=CH2)PPh2}] (3b). In contrast, 1 reacts with 2 equiv of PhC=CH to give the vinyl carbene bridged [Fe- 2(CO)(6)(mu-PPh2){mu-eta(1)(P):eta(3)(C):eta(1)(C)- (Ph)CCC(H)MeCH=CPhC(PPh2)}] (4), which results from a complex sequence of carbon-carbon and carbon-phosphorus bond formation and hydrogen migration steps
| Type: | Article |
|---|---|
| Title: | Reactions of alkynes with [Fe<sub>2</sub>(CO)<sub>6</sub>(μ-PPh<sub>2</sub>){μ-η<sup>1</sup>:η<sup>2</sup><sub>αβ</sub>(H)C<sub>α</sub>=C<sub>β</sub>=C<sub>γ</sub>H<sub>2</sub>}]: Formation of diphenylvinylphosphine-functionalized vinyl carbenes via carbon-carbon and carbon-phosphorus bond formation and hydrogen migration |
| Additional information: | Journal Article OCT 30 368NV Doherty S Univ Newcastle Upon Tyne, Dept Chem, Bedson Bldg, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England ORGANOMETALLICS |
| Keywords: | ALLENYL COMPLEXES, BOND, C-ALPHA, chemistry, COMPLEX, COMPLEXES, formation, Hydrogen, INSERTION, ligands, migration, NUCLEOPHILIC-ADDITION, PHOSPHIDO BRIDGE, RAY CRYSTAL-STRUCTURES, REACTIVITY, REGIOSELECTIVE ADDITION, S, SEQUENCE |
| UCL classification: | UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry |
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