Isolation and Ring-Opening of New 1-Sila-3-metallacyclobutanes (η⁵-C₅H₄Fe)(CO)₂CH₂SiR₂ Leading to A New Class of Organometallic Polymer

Abstract

Treatment of FpCH2SiR2Cl [Fp = (eta5-C5H5)Fe(CO)2] with lithium diisopropylamide leads to the formation of new metallacycle complexes. When R2 = Me2 and MenBu, these ring-open to form a new class of organometallic polymer. When R2 = nBu2, the metallacycle resists ring-opening and may be structurally characterized as the Ph3P-substituted species.

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

“…[126,127] Moreover, strained organoiron rings containing a single cyclopentadienyl ligand as part of the cyclic structure have been isolated and even shown to undergo ROP. [180] Strained organometallic molecules containing d-block elements are of interest in their own right as their study reveals interesting nuances in terms of structure, bonding, and reactivity, which complement the extensive results available from strained organic systems. A significant further impetus for the exploration of this area involves potential applications.…”

Iron ansa half sandwich complexes bearing a bridging distannadiyl moiety

“…Upon treatment with a mixture of BuLi and TMEDA the aromatic ring was metallated, followed by a silatropic shift of the ligand to the cyclopentadienyl ring when warmed to À45 C. Based on this protocol, Pannell et al were able to generate several iron complexes with carbonesilicon and siliconesilicon bridges, which readily undergo ROP at ambient temperature yielding polymers with molecular weights up to 175,000 g mol À1 [26,27].…”

Insertion of Chalcogens and Bis(tert-butylisonitrile)palladium(0) into a Strained Ruthenium Half-sandwich Complex

“…The second route disclosed by our group is based on a one-step synthesis starting from bimetallated halfsandwich complexes and salt metathesis with suitable bridging units [35,38]. The resulting ansa halfsandwich complexes show high ring strain, which facilitates insertion reactions [35,39] as well as ringopening polymerization reactions, as shown by Pannell and coworkers [29,30] …”