TY - JOUR
T1 - Organoiron compounds derived from the indium 'carbene analogues', [In{N(Ar)C(Me)}2CH] (Ar = dipp = 2,6-iPr2C 6H3; = Mes = 2,4,6-Me3C6H 2)
AU - Hill, Michael S.
AU - Hitchcock, Peter B.
AU - Pongtavornpinyo, Ruti
PY - 2008/5/22
Y1 - 2008/5/22
N2 - Oxidative insertion of the In(i) 'carbene analogues', [In{N(Dipp)C(Me)} 2CH] (Ar = Dipp = 2,6-iPr2C6H 3; Ar = Mes = 2,4,6-Me3C6H2) into the Fe-I bond of [CpFe(CO)2I] occurred cleanly and under mild conditions to yield the In(iii) compounds [CH{(CH3) 2CN-2,6-iPr2C6H3} 2In(I)FeCp(CO)2] and [CH{(CH3) 2CN-2,4,6-Me3C6H3} 2In(I)FeCp(CO)2], which have been fully characterised in solution and the solid state. Attempts to abstract the iodide anion from [CH{(CH3)2CN-2,6-iPr2C 6H3}2In(I)FeCp(CO)2] to form cationic species containing a coordinated indium diyl were unsuccessful and resulted in a complex mixture of products from which two ionic species were isolated. Neither cation was found to contain indium by X-ray crystallographic analysis. These observations were indicative of ill-defined decomposition pathways as have been noted by previous workers. A further attempt to form a cationic iron species containing a coordinated [In{N(Dipp)C(Me)}2CH] fragment resulted in oxidation of the iron centre from Fe(ii) to Fe(iii), with deposition of indium metal, and the isolation of a cationic Fe(iii) β-diketiminate complex.
AB - Oxidative insertion of the In(i) 'carbene analogues', [In{N(Dipp)C(Me)} 2CH] (Ar = Dipp = 2,6-iPr2C6H 3; Ar = Mes = 2,4,6-Me3C6H2) into the Fe-I bond of [CpFe(CO)2I] occurred cleanly and under mild conditions to yield the In(iii) compounds [CH{(CH3) 2CN-2,6-iPr2C6H3} 2In(I)FeCp(CO)2] and [CH{(CH3) 2CN-2,4,6-Me3C6H3} 2In(I)FeCp(CO)2], which have been fully characterised in solution and the solid state. Attempts to abstract the iodide anion from [CH{(CH3)2CN-2,6-iPr2C 6H3}2In(I)FeCp(CO)2] to form cationic species containing a coordinated indium diyl were unsuccessful and resulted in a complex mixture of products from which two ionic species were isolated. Neither cation was found to contain indium by X-ray crystallographic analysis. These observations were indicative of ill-defined decomposition pathways as have been noted by previous workers. A further attempt to form a cationic iron species containing a coordinated [In{N(Dipp)C(Me)}2CH] fragment resulted in oxidation of the iron centre from Fe(ii) to Fe(iii), with deposition of indium metal, and the isolation of a cationic Fe(iii) β-diketiminate complex.
UR - http://www.scopus.com/inward/record.url?scp=43749107101&partnerID=8YFLogxK
U2 - 10.1039/b801160e
DO - 10.1039/b801160e
M3 - Article
C2 - 18478148
AN - SCOPUS:43749107101
SP - 2854
EP - 2860
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 21
ER -