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.
A series
of palladium pincer complexes supported by (
i
Pr2P-C6H4)2CH2 (PC(sp3)H2P = bis(2-(diisopropylphosphanyl)phenyl)methane)
was isolated and characterized. Different modes of C–H activation
were observed for [{PC(sp3)H2P}PdX2] (X = Cl, OTf, Me, OAc). The thermal treatment of [{PC(sp3)H2P}PdX2] (X = Cl, OTf) induced a backbone
C–H bond activation to generate the respective [{PC(sp3)HP}PdX] complex, while under similar reaction conditions
[{PC(sp3)H2P}PdMe2] underwent a C–C
reductive elimination that led to the formation of a Pd(0) dimer,
[{PC(sp3)H2P}Pd]2. For the analogous
diacetate complex [{PC(sp3)H2P}Pd(OAc)2], the C–H activation occurred at the phosphine isopropyl
methine group to generate a palladacycle.
A square planar platinum(II)
carbene complex [{PC(sp2)P}HPt(PMe3)] ([PC(sp2)P]H = (bis[2-(di-iso-propylphosphino)phenyl]methylene)
was synthesized through the dehydrohalogenation of [{PC(sp3)HP}HPtCl] in a microwave reactor.
The tert-butyl substituted analogue, [{PC(sp2)P}
tBuPt(PMe3)] ([PC(sp2)P]
tBu =
bis[2-(di-iso-propylphosphino)-4-tert-butylphenyl]methylene), was synthesized
via an analogous route. The nucleophilic nature of the carbene carbon
was confirmed through DFT calculations and reactivity with HCl. Additionally,
[{PC(sp2)P}HPt(PMe3)] was treated with 0.5 equiv of I2 to generate a paramagnetic
product, [{PC(sp2)P}HPtI].
The Evans method and EPR spectroscopy revealed that a one-electron
oxidation occurred at the carbene carbon, thus generating a persistent
radical carbene.
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