Synthesis and Reactivity of a Cationic Platinum(II) Alkylidene Complex

Campos, Jesús; Peloso, Riccardo; Carmona, Ernesto

doi:10.1002/ange.201202655

Cited by 15 publications

(6 citation statements)

References 68 publications

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“…Both species were found in equilibrium, exhibiting A5 / A6 ratios of 4:1 and 1:2 for species a and b , respectively. A similar behavior is observed for the analogous reaction of A5c (1 bar H 2 , −30 °C to room temperature), in which A6c is obtained in a 1:3 ratio [40]. These results suggest that hydride species seem to be favored according to the basicity of the phosphine ligand.…”

Section: Reviewsupporting

confidence: 74%

“…Alternatively, Carmona and co-workers have recently described that the hydrogenation of the 16-electron Pt(II) carbene 3 bearing a cyclometalated phosphine ligand (Scheme 4) resulted in the formation of the cyclometalated complex A5c , which can be further hydrogenated to give the Pt(II) hydride A6c [40], similar to those reported by Baratta [39]. …”

Section: Reviewsupporting

confidence: 61%

“…2000 Hz, see next section), a weak interaction trans to the hydride ligand, typically an agostic contact, is supposed to exist. Carmona and co-workers also prepared quite similar complexes, A5c and A6c , where R labels represent isopropyl groups [40]. Weller and co-workers reported the formation of complex trans -[Pt(Me)(PiPr 3 ) 2 ] + A7 in which a γ-agostic interaction is located in the fourth coordination site [41].…”

Section: Reviewmentioning

confidence: 99%

“…The 1 J Pt,C is also very large for these methyl derivatives, ranging from 755 to 780 Hz (Table 2). Cyclometalated phosphine [39–40] and NHC [28,44] Pt(II) compounds were also shown to have very large 2 J Pt,H coupling constants (slightly larger than those for the non-cyclometalated versions) spanning from 107 Hz to ca. 135 Hz (average) and 1 J Pt,C values between 805 and 975 Hz.…”

Section: Reviewmentioning

confidence: 99%

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True and masked three-coordinate T-shaped platinum(II) intermediates

Ortuño¹,

Conejero²,

Lledós³

2013

Beilstein J. Org. Chem.

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SummaryAlthough four-coordinate square-planar geometries, with a formally 16-electron counting, are absolutely dominant in isolated Pt(II) complexes, three-coordinate, 14-electron Pt(II) complexes are believed to be key intermediates in a number of platinum-mediated organometallic transformations. Although very few authenticated three-coordinate Pt(II) complexes have been characterized, a much larger number of complexes can be described as operationally three-coordinate in a kinetic sense. In these compounds, which we have called masked T-shaped complexes, the fourth position is occupied by a very weak ligand (agostic bond, solvent molecule or counteranion), which can be easily displaced. This review summarizes the structural features of the true and masked T-shaped Pt(II) complexes reported so far and describes synthetic strategies employed for their formation. Moreover, recent experimental and theoretical reports are analyzed, which suggest the involvement of such intermediates in reaction mechanisms, particularly C–H bond-activation processes.

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Section: Reviewsupporting

confidence: 74%

Section: Reviewsupporting

confidence: 61%

Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

See 2 more Smart Citations

True and masked three-coordinate T-shaped platinum(II) intermediates

Ortuño¹,

Conejero²,

Lledós³

2013

Beilstein J. Org. Chem.

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“…29 Similarly, Carmona and co-workers observed a cationic platinum(II) alkylidene by NMR spectroscopy. 30,31 Yet again, structural characterization was not possible due to its instability. 30,31 Rourke and co-workers reported a non-heteroatom stabilized platinum carbene complex, with the metal attached to a 1,4dihydropyridinylene, but a resonance structure could be redrawn as protonated pyridinyl.…”

Section: ■ Introductionmentioning

confidence: 99%

Square Planar Nucleophilic and Radical Pt(II) Carbenes

2019

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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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Structure of a Reactive Gold Carbenoid

Seidel

Fürstner

2014

Angewandte Chemie

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A formal gold‐for‐chromium transmetalation allowed the gold carbenoid species [Cy3PAuCAr2]NTf2 (11) (Ar=pMeOC6H4‐) to be obtained in crystalline form. The structure in the solid state suggests that there is only little back donation of electron density from gold to the carbene center of 11 and hence very modest AuC double‐bond character; rather, it is the organic ligand framework that is responsible for stabilizing this species by resonance delocalization of the accumulated positive charge. Because 11 is capable of cyclopropanating p‐methoxystyrene even at low temperature, the discussion of its structure is deemed relevant for a better understanding of the mechanisms of π‐acid catalysis in general.

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Synthesis and Reactivity of a Cationic Platinum(II) Alkylidene Complex

Cited by 15 publications

References 68 publications

True and masked three-coordinate T-shaped platinum(II) intermediates

True and masked three-coordinate T-shaped platinum(II) intermediates

Square Planar Nucleophilic and Radical Pt(II) Carbenes

Structure of a Reactive Gold Carbenoid

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