Intramolecular Si−Si Bond Activation by the Iron Carbonyl Unit in an (η⁴-Silole)tricarbonyliron Complex

Abstract

Intramolecular actiVation of the Si-Si bond linked to an η 4 -silole ligand by a metal center was obserVed when 1,1-bis(trimethylsilyl)tetraphenylsilole was heated with Fe(CO) 5 in refluxing p-xylene, to produce η 4 -(1-trimethylsilyl-1-methyltetraphenylsilole)Fe(CO) 3 as the final product.Si-Si bonds are very thermally stable, sometimes even comparable to a C-C bond, but can easily be activated by transition metals. 1,2 This property has most frequently been observed in intramolecular processes, which has led to many intriguing reactions in recent years. [3][4][5][6][7][8][9] To date, many studies of such reactions have focused on systems containing Si-Si bonds directly linked to transition metals, initially observed independently by Pannell's and Ogino's groups in 1986. 4,5 Also studied have been systems in which the Si-Si bonds are linked indirectly to a metal atom through an η 1 -methylene ligand, a

Synthesis and Properties of Structural Variants of the Si−Si Bridged Bis(cyclopentadienyl)tetracarbonyldiiron Complexes: Modification on the Bridge

“…This result remained unchanged even after substitution of a CO ligand with P(OPh) 3 , which has been well known to be able to accelerate the thermal rearrangement . This means that the C−Si bond could not be activated by the iron center, according to the previously suggested mechanism of thermal rearrangement, which is also in accordance with the notion that the C−Si bond should be much more difficult to activate by transition metals than Si−Si bonds …”