Selective homogeneous catalytic hydrogenation of polynuclear aromatics

Grey, Roger A.; Pez, Guido P.; Wallo, Andrea

doi:10.1021/ja00538a061

Cited by 72 publications

(7 citation statements)

References 3 publications

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“…The chemistry of anionic transition metal complexes is of significant interest due to their nucleophilic reactivity toward organic molecules, their utilization in the preparation of homo- and heteronuclear transition metal clusters, and their reactivity as alkylating reagents with various electrophiles , and as reducing hydride donors with polar molecules. – Formation of relatively stable anionic complexes in the absence of strong π-accepting ligands, capable of lowering the electron density at the metal center by enhancing back-bonding, is generally difficult, and relatively few examples of such compounds are known. ,,,,– …”

Section: Resultsmentioning

confidence: 99%

Cationic, Neutral, and Anionic Platinum(II) Complexes Based on an Electron-Rich PNN Ligand. New Modes of Reactivity Based on Pincer Hemilability and Dearomatization

et al. 2008

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The synthesis and reactivity of new Pt(II) complexes, including anionic d8 complexes, based on the electron-rich, hemilabile PNN-type pincer ligand C5H3N-2-(CH2PtBu2)(CH2NEt2) are described. Formation of these complexes involves dearomatization/aromatization processes of the ligand. The chloride complex [(PNN)PtCl]+Cl− (1) was prepared and reacted with the base tBuOK to give the deprotonated, neutral chloride complex (PNN*)PtCl (2) (PNN* = C5H3N-2-(CHPtBu2)(CH2NEt2)). Reaction of 2 with nBuLi gave the corresponding neutral hydride complex (PNN*)PtH (3), which was readily protonated by triflic acid to give the cationic hydride complex [(PNN)PtH]+OTf− (4). Unexpectedly, reaction of complex 2 with 1 equiv of RLi resulted in opening of the chelate ring, to give the corresponding anionic, dearomatized complexes Li+[(PNN*)Pt(Cl)(R)]− (R = methyl, 5; phenyl, 6). Notably, these complexes are relatively stable although they bear no stabilizing π acceptors that can lower the electron density at the metal center. Complexes 5 and 6 readily undergo protonation by HCl to form the corresponding neutral, aromatic complexes (PNN)Pt(Cl)(R) (R = methyl, 7; phenyl, 8), in which the hemilabile amine “arm” remains decoordinated and does not undergo protonation. Minor amounts of the dearomatized chloride complex 2 are also formed as a result of elimination of RH. Reaction of complexes 5 and 6 with water results in selective protonation−aromatization to give the corresponding complexes 7 and 8.

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Section: Resultsmentioning

confidence: 99%

Cationic, Neutral, and Anionic Platinum(II) Complexes Based on an Electron-Rich PNN Ligand. New Modes of Reactivity Based on Pincer Hemilability and Dearomatization

et al. 2008

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“…Selective hydrogenation of specific double bonds or the hydrogenation of only one aromatic ring when several are present has been far less successful. Hydrogenation of only one ring of multicyclic aromatics and selective hydrogenation of a single double bond of perinaphthylene or perianthracene have been accomplished using a rhodium cluster catalyst. , …”

Section: Resultsmentioning

confidence: 99%

“…Hydrogenation of only one ring of multicyclic aromatics and selective hydrogenation of a single double bond of perinaphthylene or perianthracene have been accomplished using a rhodium cluster catalyst. 16,17 Experimental Section General Procedures. 1 was synthesized via literature procedures.…”

Section: Resultsmentioning

confidence: 99%

Germylene-Induced Hydrogenation of Benzophenone

et al. 2003

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Ge[CH(SiMe 3 ) 2 ] 2 reacts with benzophenone to form a conjugated triene. Wilkinson's catalyst, Rh-(PPh 3 ) 3 Cl, is an effective precatalyst for the isomerization of one double bond and hydrogenation of a second double bond of this triene. This reaction demonstrates that germylene activation of the phenone moiety yields reactive double bonds amenable to catalytic transformation, even with bulky catalysts such as the presumed active form of Wilkinson's catalyst, Rh(PPh 3 ) 2 Cl.Supporting Information Available: Tables giving X-ray crystallographic data for compound 4; these data are also available as CIF files. This material is available free of charge via the Internet at http://pubs.acs.org.

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“…69,[117][118][119] The partial hydrogenation of polyaromatic compounds, such as anthracene, 9-methylanthracene, and 9-trifluoroacetylanthracene to the 1,2,3,4-tetrahydroanthrocene derivative, can be accomplished with [Rh(DPPE)(arene)] +115 and ruthenium hydride complexes with triphenylphosphine ligands. [120][121][122][123][124] Partial hydrogenation of polyaromatics can also be achieved with [Co 2 (CO) 8 ] under carbon monoxide and hydrogen but an isolated benzene nucleus will not reduce. [125][126][127] H 2 (197 atm) [Co 2 (CO) 8 ] 135 °C…”

Section: Dienes To Alkenes By 14-reductionmentioning

confidence: 99%

8.17 Homogeneous Catalytic Hydrogenation of CåC and CåC

Ager¹

2014

Comprehensive Organic Synthesis II

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Selective homogeneous catalytic hydrogenation of polynuclear aromatics

Cited by 72 publications

References 3 publications

Cationic, Neutral, and Anionic Platinum(II) Complexes Based on an Electron-Rich PNN Ligand. New Modes of Reactivity Based on Pincer Hemilability and Dearomatization

Cationic, Neutral, and Anionic Platinum(II) Complexes Based on an Electron-Rich PNN Ligand. New Modes of Reactivity Based on Pincer Hemilability and Dearomatization

Germylene-Induced Hydrogenation of Benzophenone

8.17 Homogeneous Catalytic Hydrogenation of CåC and CåC

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