Cyclometallation reactions in neopentyl and trimethylsilylmethyl systems of rhodium(III) and iridium(III). Formation and X-ray crystal structures of the four-membered metallacycles [Rh(CH₂CMe₂CH₂)(η⁵-C₅Me₅)(PPh₃)] and [Ir(CH₂SiMe₂CH₂)(η⁵-C₅Me₅)(PPh₃)]

Abstract

1.58 (d, 2) 6.75-7.70 (m) (4) CRh(CH2SiMe3)2(rl 5-C5Me5)(PPh3)l 0.10 (s) 0.25 (m) 1.40 (d, 2.5) 6.85-7.6 (m) 0.68 (dd, 3, 6) 1.44 (d, 2) -6.85-7.5 (m) (5) CIr(CH,SiMe,),(rlS-C,Mes)(~~~~~l 0.13 (s) (6) [Ir(CH,SiMe,CH,)(q5-C5Me5)(PPh3)] -0.28 (dd, 8, 11) -0.62 (s) 0.15 (s) 1.45 (d, 2) 6.85-7.8 (m)

Structural and Redox Properties of Novel Spirocyclic 1-Sila-3-ferracyclobutanes, [(η5-C5H4)Fe(L2)CH2SiMe2], L2 = P−P (diphosphine)

“…Sila-metallacyclobutanes containing a transition metal atom have been explored in terms of their synthesis and reactivity (M = Ti, Zr, Hf, Nb, Mo, Ir) undergo ring expansion chemistry via insertion of such reagents as paraformaldehyde, isocyanides, and carbon monoxide into the M−C bond.…”

Modeling the Proposed Intermediate in Alkane Carbon−Hydrogen Bond Activation by Cp*(PMe3)Ir(Me)OTf: Synthesis and Stability of Novel Organometallic Iridium(V) Complexes

“…However, iridium(V) compounds such as 3 are rare, calling into question the likelihood of this mechanism. Although there are a number of reports that invoke the intermediacy of iridium(V) complexes along reaction pathways, − only a few organometallic iridium(V) complexes have been isolated to date. ,− …”

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

“…Well-defined polymers containing transition metal atoms in the backbone are attractive materials owing to their potential applications as catalysts, ion-exchange resins, polymeric support materials, precursors for ceramic materials, conducting polymers, , and chemical sensors . Excellent examples of such materials are the high-molecular-weight poly-silyleneferrocenylenes obtained from the ring-opening of the appropriate strained [1]-sila-ferrocenophanes. , There are reports on the synthesis and reactivity of 1-sila-3-metallacyclobutanes (metal = Zr, Nb, and Mo, and Ir) that undergo ring expansion upon reaction with paraformaldehyde,7c isocyanides,7d and CO 7e. Furthermore, a recent example of 1-sila-2-platinacyclobutanes that exhibits a diphenylsilane insertion has been reported .…”