The photolysis of Fe(CO)3{P(OPh)3}2 and reaction of the photoproduct with alkynes: crystal structures of Fe(CO)2{P(OPh)3}2(η2-PhCCPh), Fe(CO)2{P(OPh)3}2{η1:η1-C(O)C(Me)C[CH(OEt)2]C(O)} and Fe2(CO)4{P(OPh)3}2(PhCCH)2
| Autor: | Desmond Cunningham, Patrick McArdle, Anthony R. Manning, Natalie L. Cromhout, M. Barrow |
|---|---|
| Rok vydání: | 2000 |
| Předmět: |
chemistry.chemical_classification
Iron hydride Stereochemistry Ligand Organic Chemistry Alkyne Crystal structure Biochemistry Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound Trigonal bipyramidal molecular geometry chemistry Octahedron Materials Chemistry Moiety Physical and Theoretical Chemistry Derivative (chemistry) |
| Zdroj: | Journal of Organometallic Chemistry. 612:61-68 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/s0022-328x(00)00384-3 |
| Popis: | UV-irradiation of Fe(CO) 3 {P(OPh) 3 } 2 ( 1 ) afforded an orthometallated iron hydride HFe(CO) 2 {P(OPh) 3 }{(PhO) 2 POC 6 H 4 } ( 2 ) which was reacted in situ with alkynes R 1 CCR 2 . Internal alkynes reacted to give either η 2 -alkyne Fe(CO) 2 {P(OPh) 3 } 2 (η 2 -R 1 CCR 2 ) [ 3a , R 1 =R 2 =Ph; 3b , R 1 =Ph, R 2 =CH(OEt) 2 ] or maleoyl Fe(CO) 2 {P(OPh) 3 } 2 {η 1 :η 1 -C(O)C(R 1 )C(R 2 )C(O)} [ 4a , R 1 =Ph, R 2 =Me; 4b , R 1 =R 2 =Me; 4c , R 1 =Me, R 2 =CH(OEt) 2 ; 4d , R 1 =Me, R 2 =CH 2 OH; 4e , R 1 =R 2 =CH 2 OH] complexes. The terminal alkyne HCCPh reacted with 2 to give the ferrole derivative Fe 2 (CO) 4 {P(OPh) 3 } 2 (PhCCH) 2 ( 5 ). The crystal structures of 3a , 4c and 5 were determined. Complex 3a is trigonal bipyramidal about the iron atom with trans apical phosphite ligands and an equatorial arrangement of the CO groups and alkyne CC moiety. Complex 4c is octahedral with trans phosphite ligands and cis carbonyl groups. The alkyne ligand has undergone double carbonylation to generate a ferracyclopentenedione (maleoyl) ring that occupies the remaining two coordination sites at the metal centre. Complex 5 is formally a derivative of Fe 2 (CO) 9 in which an Fe(CO) 2 {P(OPh) 3 } moiety is π-bonded to a ferracyclopentadiene ring arising from the tail-to-tail coupling of two HCCPh ligands. |
| Databáze: | OpenAIRE |
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