Transition metal–carbon bonds. Part 52. Large ring and cyclometallated complexes formed from But2PCH2CH2CHRCH2CH2PBut2(R  H or Me) and IrCl3, or [Ir2Cl4(cyclo-octene)4] : crystal structures of the cyclometallated hydride, [IrHCl(But2PCH2CH2CHCH2CH2PBut2)], and the carbene complex [IrCl(Bu<

Crocker, Christopher; Empsall, H. David; Errington, R. John; Hyde, Eileen M.; McDonald, Walter S.; Markham, Richard; Norton, Michael C.; Shaw, Bernard L.; Weeks, Brian

doi:10.1039/dt9820001217

Cited by 78 publications

(35 citation statements)

References 2 publications

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“…Hydrated IrCl 3 also cyclometalates the potentially P,C,P-tridentate coordinating ligand precursor 26d to yield the iridium(III) complex 257 (Scheme 107). 107,373 Substitution of the chloride in 257…”

Section: Scheme 101mentioning

confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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Section: Scheme 101mentioning

confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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“…However, also for other late metals α‐H‐elimination has been reported in works from e. g. Shaw in which PC(sp 3 )P ligand 53 reacts with IrCl 3 to generate iridium hydrido chloride complex 54 , and subsequently iridium carbene 55 is generated upon heating complex 54 ( Scheme 10). [38–43] …”

Section: α‐Eliminations Cleaving C−c Bondsmentioning

confidence: 99%

α‐ and β‐Eliminations in Transition Metal Complexes: Strategies to Cleave Unstrained C−C and C−F Bonds

Karimzadeh

Wendt

2021

Helvetica Chimica Acta

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Oxidative addition is the standard process for single‐bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ‐bonds e. g. C(sp3)−F and C(sp3)−C(sp3) bonds are the exceptions in this respect. This short review aims at demonstrating how both α‐ and β‐eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α‐ and β‐eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β‐eliminations is controlled by the s‐character of the participating bonds where a higher s‐character gives a better overlap in the multi‐center transition state thereby increasing the reactivity; still β‐aryl eliminations can compete with the classical β‐hydrogen eliminations in certain cases.

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“…However, they also have lower reactivity due to a less polarized M═E bond, which cannot activate strong C–H or related bonds. Though H–H addition across Ir═C bonds has been reported, this almost certainly occurs by oxidative addition of H 2 at the Ir(I) center followed by hydride migration [64,79–80]. The well-developed C–H borylation chemistry of Hartwig and others provides an indication that cooperation may be operative to some extent in the activation of C–H bonds at metal boryls [81–84], though the exact mechanism of C–H cleavage seems to depend on the nature of the metal catalyst.…”

Section: Reviewmentioning

confidence: 99%

Metal–ligand multiple bonds as frustrated Lewis pairs for C–H functionalization

Whited¹

2012

Beilstein J. Org. Chem.

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SummaryThe concept of frustrated Lewis pairs (FLPs) has received considerable attention of late, and numerous reports have demonstrated the power of non- or weakly interacting Lewis acid–base pairs for the cooperative activation of small molecules. Although most studies have focused on the use of organic or main-group FLPs that utilize steric encumbrance to prevent adduct formation, a related strategy can be envisioned for both organic and inorganic complexes, in which "electronic frustration" engenders reactivity consistent with both nucleophilic (basic) and electrophilic (acidic) character. Here we propose that such a description is consistent with the behavior of many coordinatively unsaturated transition-metal species featuring metal–ligand multiple bonds, and we further demonstrate that the resultant reactivity may be a powerful tool for the functionalization of C–H and E–H bonds.

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Abstract: H or Me) and lrC13, or [Ir,Cl,(cycl~-octene)~] : Crystal Structures of the Cyclometal lated Hydride, [ ir H CI ( But2 k H 2 C H 2 d H C H2C H2 6Butp)], and the Carbene Complex [ l h ( But2bCH2CH2&CH2CH2bBuf2)] t

Cited by 78 publications

References 2 publications

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

α‐ and β‐Eliminations in Transition Metal Complexes: Strategies to Cleave Unstrained C−C and C−F Bonds

Metal–ligand multiple bonds as frustrated Lewis pairs for C–H functionalization

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