Square Planar Nucleophilic and Radical Pt(II) Carbenes

Deziel, Anthony P.; Hoffbauer, Melissa R.; Iluc, Vlad M.

doi:10.1021/acs.organomet.8b00864

Cited by 9 publications

(3 citation statements)

References 61 publications

(122 reference statements)

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“…We have been studying group 10 metal carbenes supported by [PC(sp 2 )P] ((bis[2-(di-isopropylphosphino)phenyl]methane)) and discovered new reactivity patterns for late transition metal carbenes. − The rich reactivity observed for these carbenes − prompted us to expand our studies to iron − and probe the reactivity of the corresponding compounds. Herein, we report the synthesis of [{PC(sp 2 )P}Fe(N 2 )(PMe 3 )] ( 1-N 2 -PMe 3 ) and its unprecedented [2+2] reactivity with alkynes to produce η 3 -vinyl carbene iron complexes, [{PC(C Ph C(sp 2 ) Ph }Fe(L)] ( 2-L , L = N 2 , PMe 3 , Figure E).…”

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confidence: 99%

[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

Hoffbauer

Iluc

2021

J. Am. Chem. Soc.

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Ruthenium carbenes, famously used in olefin metathesis, have impacted numerous research areas, ranging from synthesis to materials and biology. Although in the same group as ruthenium, iron carbenes showing similar reaction patterns have not been reported. Such targets are of high interest because the use of a sustainable metal would lead to a decreased cost, toxicity, and environmental impact of the corresponding compounds. Herein, we report the synthesis of an iron carbene complex, [{PC(sp2)P}Fe(N2)(PMe3)] ([PC(sp2)P] = (bis[2-(di-isopropylphosphino)phenyl]methylene), which is capable of performing [2+2] cycloaddition reactions in the presence of alkynes. Specifically, η3-vinyl carbenes are formed stoichiometrically through a [2+2] cycloaddition between the alkyne and the metal carbene. Additional reactivity of the η3-vinyl carbenes with alkynes yields a second insertion product containing a new iron carbene moiety.

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[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

Hoffbauer

Iluc

2021

J. Am. Chem. Soc.

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“… 25 Consequently, carbenes as redox-active/noninnocent ligands were ideal targets. The group of Iluc has extensively studied the redox properties of such PCP pincer complexes featuring a central redox-noninnocent diarylcarbene moiety for Fe, 26 Ni, 27 Pt, 28 and Pd 29 complexes. The PCP ligand can adopt three oxidation states ( Figure 5 ).…”

Section: Pc Carbene P Pincer Complexesmentioning

confidence: 99%

Carbene Radicals in Transition-Metal-Catalyzed Reactions

et al. 2023

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Discovered as organometallic curiosities in the 1970s, carbene radicals have become a staple in modern-day homogeneous catalysis. Carbene radicals exhibit nucleophilic radical-type reactivity orthogonal to classical electrophilic diamagnetic Fischer carbenes. Their successful catalytic application has led to the synthesis of a myriad of carbo- and heterocycles, ranging from simple cyclopropanes to more challenging eight-membered rings. The field has matured to employ densely functionalized chiral porphyrin-based platforms that exhibit high enantio-, regio-, and stereoselectivity. Thus far the focus has largely been on cobalt-based systems, but interest has been growing for the past few years to expand the application of carbene radicals to other transition metals. This Perspective covers the advances made since 2011 and gives an overview on the coordination chemistry, reactivity, and catalytic application of carbene radical species using transition metal complexes and catalysts.

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“…1 The design of a suitable molecular scaffold that provides steric protection to the MCR 2 fragment has been crucial for their stabilisation and, with the exception of Templeton's Pt( iv ) methylidene complex supported by a tris(pirazolyl)borate ligand, 2 chelating P-donating ligands of high steric demand have proved effective for this purpose. Noticeably, the satisfactorily characterised non-heretoatom-substituted alkylidene complexes of Pt( ii ) and Pt(0) (Chart 1) bear di(isopropyl)-substituted phosphines as ancillary ligands, and were reported only recently by some of us in 2012, 3 and some years later by Iluc 4 and Piers. 5…”

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confidence: 96%