Insertion into the Strained Silicon−Carbon Bond of a Silicon-Bridged [1]Ferrocenophane:  Synthesis and Structure of a [2]Platinasilaferrocenophane

Abstract

The first example of a well-characterized insertion of a transition-metal fragment into a strained silicon-carbon bond of a silicon-bridged [1]ferrocenophane is reported. Reaction of Fe(η-C5H4)2SiMe2 (3) with Pt(PEt3)3 yields the novel amber crystalline [2]platinasilaferrocenophane Fe(η-C5H4)2Pt(PEt3)2SiMe2 (4). An X-ray diffraction study of 4 indicated that the cyclopentadienyl rings in this species are tilted with respect to one another by an angle of 11.6(3)°. Complex 4 is of interest as a model of the proposed intermediate during the transition-metal-catalyzed ring-opening polymerization of species such as 3 to yield poly(ferrocenylsilanes).

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

“…[92][93][94] Notably, the FeÀCp bond in sila [1]ferrocenophanes has been shown to be susceptible to a reduction of hapticity and ultimately cleavage with photoirradiation in the presence of weak bases such as [C 5 H 4 R] À (R = H, Me). [48,61,63] Germanium and Tin…”

Photoinduced iron–cyclopentadienyl (Fe–Cp) bond cleavage reactions and photocontrolled polymerizations of strained [1]ferrocenophanes

“…Sila [1]ferrocenophanes also undergo thermal [22], anionic [23] or transition metal catalyzed [24] ringopening polymerizations (ROP), to give polyferrocenylsilanes (PFS) through cleavage of the ipso-Cp-Si bond. When reacted with Pt(0) complexes, sila [1]ferrocenophanes yield platinasila [2]ferrocenophanes by insertion of a Pt fragment into the Si-Cp bond [25].…”

Polyferrocenylsilane‐Based Polymer Systems

“…[b] Three independent molecules in the unit cell. [18] [Fe(h 5 -C 5 H 4 ) 2 SiR 2 OSiR 2 ], R = Me or Ph 2.5(12) [45] [Fe(h 5 -C 5 H 4 ) 2 SiMe 2 (OSiMe 2 ) x ], x = 2 or 3 1.5(5) [45] [Fe(h 5 -C 5 H 4 ) 2 Pt(PEt 3 ) 2 SiMe 2 ] 11.6(3) [47] [Fe(h 5 5.9(6) [48] [Fe(h 5 11.4(7) [58] [(h 5 [54] SiMe{Co 2 (CO) 6 C 2 nBu} 19.51(19) [54] Si{Co 2 (CO) 6 C 2 nBu} 2 19.87(22) [54] SiMe{Mo 2 Cp 2 (CO) 4 C 2 Ph} 20.93(20) [54] SiMeCo(CO) 4 19.98(5) [55] SiMe{Ni 2 (Cp) 2 C 2 Ph} 21.21(21) [56] SiMe{Ni(dppe)C 2 Ph} [a] 20.38(10) [54] SiMe{Ni(dmpe)C 2 Ph} [a] 19.90(13) [54] [a] dmpe = 1,2-bis(dimethylphosphino)ethane.…”