Issue 30, 2010

Phosphine induced migratory COinsertion into the Fe–CH2 bond of the organometallic polymer -[(η5-C5H4)Fe(CO)2CH2SiMe2]n- and characterization of model iron complexes

Abstract

Thermal and photochemical treatment of 1-sila-3-ferracyclobutane, (η5-[upper bond 1 start]C5H4)Fe(CO)2CH2Si[upper bond 1 end]Me2 (1) results in ring-opening polymerization (ROP). Phosphine-induced migratory CO insertion into the Fe–CH2 bond of the preformed polymer, -[(η5-C5H4)Fe(CO)2CH2SiMe2]n- (2) results in either linear polymers, -[(η5-C5H4)Fe(CO)(PR3)C(O)CH2SiMe2]n- [R3 = Me2Ph (3), Ph3 (4)] or diphosphine bridged polymers, -{[(η5-C5H4)Fe(CO)C(O)CH2SiMe2]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, {[(η5-C5H5)Fe(CO)C(O)CH3]2P–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.

Graphical abstract: Phosphine induced migratory CO insertion into the Fe–CH2 bond of the organometallic polymer -[(η5-C5H4)Fe(CO)2CH2SiMe2]n- and characterization of model iron complexes

Supplementary files

Article information

Article type
Paper
Submitted
09 Dec 2009
Accepted
05 May 2010
First published
04 Jun 2010

Dalton Trans., 2010,39, 7125-7131

Phosphine induced migratory CO insertion into the Fe–CH2 bond of the organometallic polymer -[(η5-C5H4)Fe(CO)2CH2SiMe2]n- and characterization of model iron complexes

M. Kumar, A. J. Metta-Magana, H. K. Sharma and K. H. Pannell, Dalton Trans., 2010, 39, 7125 DOI: 10.1039/B925936H

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