Phosphine induced migratory CO insertion into the Fe-CH2 bond of the organometallic polymer -[(eta(5)-C5H4)Fe(CO)2CH2SiMe2]n- and characterization of model iron complexes.
Thermal and photochemical treatment of 1-sila-3-ferracyclobutane, (eta(5)C(5)H(4))Fe(CO)(2)CH(2)SiMe(2) (1) results in ring-opening polymerization (ROP). Phosphine-induced migratory CO insertion into the Fe-CH(2) bond of the preformed polymer, -[(eta(5)-C(5)H(4))Fe(CO)(2)CH(2)SiMe(2)](n)- (2) results in either linear polymers, -[(eta(5)-C(5)H(4))Fe(CO)(PR(3))C(O)CH(2)SiMe(2)](n)- [R(3) = Me(2)Ph (3), Ph(3) (4)] or diphosphine bridged polymers, -{[(eta(5)-C(5)H(4))Fe(CO)C(O)CH(2)SiMe(2)](2)(P-P)}(n)- [P-P = dppe (5), dppp (6), dppb (7), trans-dppen (8), dmpe (9); dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,2-bis(diphenylphosphino)propane, dppb = 1,2-bis(diphenylphosphino)butane, cis-dppen = cis-1,2-bis(diphenylphosphino)ethylene, dmpe = 1,2-bis(dimethylphosphino)ethane]. The analogous model complexes, {[(eta(5)-C(5)H(5))Fe(CO)C(O)CH(3)](2)P-P} [P-P = dppp (10), dppb (11), trans-dppen (12), dmpe (13)] were synthesized and characterized as models of the acylated polymers. The X-ray crystal structure of 11 and 13 were determined to establish the bridging nature of the diphosphines in the model complexes and to get insight of the crystal packing.
Kumar
Mukesh
M
Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968-0513, USA.
Metta-Magana
A J
AJ
Sharma
Hemant K
HK
Pannell
Keith H
KH
D002248:Carbon Monoxide / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010720:Phosphines / Q000737:chemistry*; D010777:Photochemistry; D011108:Polymers / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013696:Temperature
D005296:Ferrous Compounds; D010720:Phosphines; D011108:Polymers; D012821:Silanes; D002248:Carbon Monoxide; C044646:phosphine