Novel T‐Shaped 14‐Electron Platinum(<scp>II</scp>) Complexes Stabilized by One Agostic Interaction

Baratta, Walter; Stoccoro, Sergio; Doppiu, Angelino; Herdtweck, Eberhardt; Zucca, Antonio; Rigo, Pierluigi

doi:10.1002/ange.200390003

Cited by 58 publications

(58 citation statements)

References 40 publications

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“…[143] A recent example from platinum chemistry also illustrates that apparently three-coordinate aryl Pt II complexes 64 a and 64 b are in fact square planar complexes stabilized through an agostic interaction with one of the methyl groups of the phosphane ligand. [202] Since it was recognized that complexes with bulky ligands can catalyze the Stille and other coupling reactions with less active organic nucleophiles, such as chlorides or triflates (see Section 2.6), the number of examples of such complexes has increased. [203,204] From a practical point of view, a formally 16-electron agostic complex, with very high nucleophilicity and Scheme 36.…”

Section: Proposals For Dissociative Mechanismsmentioning

confidence: 99%

The Mechanisms of the Stille Reaction

2004

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Eighteen years ago in Angewandte Chemie John K. Stille reviewed a novel methodology, which eventually became known by his name, for the coupling of organostannanes with organic electrophiles. Since then that seed has blossomed into a multifaceted methodology full of hidden possibilities to explore, discover, and enjoy. Very recent modifications are making synthetic wishes come true that were only dreamed of a few years ago. Moreover, as important advances are being made in the understanding of the mechanistic details of the process, it is becoming increasingly possible to apply this essential reaction and its new variants in a less empirical way. The purpose of this Review is to give a critical account of this progress.

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Section: Proposals For Dissociative Mechanismsmentioning

confidence: 99%

The Mechanisms of the Stille Reaction

2004

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“…[7] With PPh 2 (2,6-Me 2 C 6 H 3 ), cyclometalation reactions occur readily with platinum, [5] ruthenium, [8] and osmium, [9] producing stable compounds, each containing a carbon-metal s bond. Interestingly, with the last of these metals a tridentate trans-stilbene-type ligand (Figure 1) is formed through a dehydrogenative carbon À carbon coupling of two phosphane methyl groups, which represents an intriguing mode for the functionalization of hydrocarbon groups mediated by metal centers.…”

Section: A C H T U N G T R E N N U N G [Barmentioning

confidence: 99%

“…[3] Recently, by employment of the dimethyl-substituted phosphane PR 2 (2,6-Me 2 C 6 H 3 ) (R= Ph, Cy) we have isolated rare examples of 14-electron complexes of d 6 ruthenium [4] and d 8 platinum, [5] stabilized through d-agostic interactions of the ortho-methyl groups (nonclassical M···h 3 -H 2 C interaction mode) (Figure 1). [6] Abstract: The Vaska-type iridium(I) complex [IrCl(CO)A C H T U N G T R E N N U N G {PPh 2 A C H T U N G T R E N N U N G (2-MeC 6 H 4 )} 2 ]…”

Section: Introductionmentioning

confidence: 99%

CH Activation and CC Double Bond Formation Reactions in Iridium ortho‐Methyl Arylphosphane Complexes

Baratta

Ballico

Zotto

et al. 2007

Chemistry A European J

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The Vaska-type iridium(I) complex [IrCl(CO){PPh(2)(2-MeC(6)H(4))}(2)] (1), characterized by an X-ray diffraction study, was obtained from iridium(III) chloride hydrate and PPh(2)(2,6-MeRC(6)H(3)) with R=H in DMF, whereas for R=Me, activation of two ortho-methyl groups resulted in the biscyclometalated iridium(III) compound [IrCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)] (2). Conversely, for R=Me the iridium(I) compound [IrCl(CO){PPh(2)(2,6-Me(2)C(6)H(3))}(2)] (3) can be obtained by treatment of [IrCl(COE)(2)](2) (COE=cyclooctene) with carbon monoxide and the phosphane in acetonitrile. Compound 3 in CH(2)Cl(2) undergoes intramolecular C-H oxidative addition, affording the cyclometalated hydride iridium(III) species [IrHCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}] (4). Treatment of 2 with Na[BAr(f) (4)] (Ar(f)=3,5-C(6)H(3)(CF(3))(2)) gives the fluxional cationic 16-electron complex [Ir(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)][BAr(f) (4)] (5), which reversibly reacts with dihydrogen to afford the delta-agostic complex [IrH(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}][BAr(f)(4)] (6), through cleavage of an Ir-C bond. This species can also be formed by treatment of 4 with Na[BAr(f)(4)] or of 2 with Na[BAr(f)(4)] through C-H oxidative addition of one ortho-methyl group, via a transient 14-electron iridium(I) complex. Heating of the coordinatively unsaturated biscyclometalated species 5 in toluene gives the trans-dihydride iridium(III) complex [IrH(2)(CO){PPh(2)(2,6-MeC(6)H(3)CH=CHC(6)H(3)Me-2,6)PPh(2)}][BAr(f) (4)] (7), containing a trans-stilbene-type terdentate ligand, as result of a dehydrogenative carbon-carbon double bond coupling reaction, possibly through an iridium carbene species.

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“…490,491 This interaction is labile and in the presence of weak donors like THF, a 16e complex is formed due to donor coordination.…”

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confidence: 99%

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

2009

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Novel T‐Shaped 14‐Electron Platinum(II) Complexes Stabilized by One Agostic Interaction

Cited by 58 publications

References 40 publications

The Mechanisms of the Stille Reaction

The Mechanisms of the Stille Reaction

CH Activation and CC Double Bond Formation Reactions in Iridium ortho‐Methyl Arylphosphane Complexes

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

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