Insertion and oxidative addition reactions of rhodium porphyrin complexes. Novel free radical chain mechanisms

Paonessa, Ralph S.; Thomas, Nicholas C.; Halpern, Jack

doi:10.1021/ja00300a044

Cited by 105 publications

(72 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The above results might seem conflicting with reported insertion reactions of CO, olefins, aldehydes, and isocyanides into the RhÀ ÀH bonds of the less hindered complexes [Rh III (OEP)(H)] and [Rh III (TPP)(H)] (141,(143)(144)(145)(146)(147)(148)(149)(150). Since [Rh III (por)(H)] species lack any cis vacant sites, these insertion reactions are quite remarkable and do not likely proceed via a common (migratory) insertion requiring coordination of the CO, CNR, or olefinic substrates cis to the RhÀ ÀH bond.…”

Section: Radicaloid Insertions Into (Por)rhà àH Bondsmentioning

confidence: 63%

“…44). The acyl radical contribution to the electronic structure of [Rh II (por)(CO)] species also allows hydrogen radical abstraction reactions from (OEP)RhÀ ÀH bonds (only for the least hindered OEP complexes) (141), and H 2 or HSn(Bu) 3 (with formation of [Sn(Bu) 3 ] 2 ) to form the formyl species [Rh III (por)(C(O)H)] (139). Binuclear coupling of two RhÀ ÀC(O).…”

Section: Reactions With Comentioning

confidence: 99%

“…The reaction of [Rh II (OEP)] with styrene was claimed to proceed via a radical chain mechanism (141 (Fig. 48).…”

Section: Reactions With Alkenes and Alkynesmentioning

confidence: 99%

See 2 more Smart Citations

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Bruin

Hetterscheid

Koekkoek

et al. 2007

Progress in Inorganic Chemistry

121

View full text Add to dashboard Cite

Section: Radicaloid Insertions Into (Por)rhà àH Bondsmentioning

confidence: 63%

Section: Reactions With Comentioning

confidence: 99%

See 1 more Smart Citation

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Bruin

Hetterscheid

Koekkoek

et al. 2007

Progress in Inorganic Chemistry

121

View full text Add to dashboard Cite

“…The reaction of [Rh II -(OEP)] with styrene was claimed to proceed by a radical chain mechanism. [56] In Other alkenes like acrylates [57] give similar alkyl-bridged species [ Figure 15. The reactivity of [M II (por)] species changes from M-C to C-C coupling to no coupling at all upon increasing the steric bulk.…”

Section: (Electronic) Structure Of Neutral 17-ve M Ii (Alkene)(por) Rmentioning

confidence: 99%

Paramagnetic (Alkene)Rh and (Alkene)Ir Complexes: Metal or Ligand Radicals?

Bruin

Hetterscheid

2007

Eur J Inorg Chem

View full text Add to dashboard Cite

Keywords: Rhodium / Iridium / Alkene ligands / Metallo-radicals / Ligand radicals In this review a detailed overview is given of the (electronic) structure and reactivity of open-shell (paramagnetic) alkene rhodium and iridium complexes M x (alkene) (M = Rh, Ir; x = 0, +II). In most cases these species are highly reactive, but some notable exceptions of stable species for which not much reactivity has been described are also included (section 2). coupling reactions with a series of other radicals, as well as metal-based allylic hydrogen atom abstractions from M II (α-alkene) species. On the other hand, (donor induced) ligand radical character is crucial in a variety of M-C and C-C radical coupling reactions, C-O bond formation by oxygenation of M II (alkene) species and alkene "insertions" into (por)M-H bonds. The review concludes with some speculations about possible roles of paramagnetic M(olefin) (M = Rh, Ir) species in catalytic olefin oxygenation and carbene transfer reactions.

show abstract

“…(18)) [37]. The (por)Rh-H reactions are catalyzed by (por)Rh IIÅ species and proceed by a radical chain pathway involving…”

Section: Reactions Of (Por)m-h With Co (M = Rh Ir)mentioning

confidence: 99%

Factors contributing to one-electron metalloradical activation of ethene and carbon monoxide illustrated by reactions of Co(II), Rh(II), and Ir(II) porphyrins

Cui

Wayland

2007

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Insertion and oxidative addition reactions of rhodium porphyrin complexes. Novel free radical chain mechanisms

Cited by 105 publications

References 0 publications

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Paramagnetic (Alkene)Rh and (Alkene)Ir Complexes: Metal or Ligand Radicals?

Factors contributing to one-electron metalloradical activation of ethene and carbon monoxide illustrated by reactions of Co(II), Rh(II), and Ir(II) porphyrins

Contact Info

Product

Resources

About