Alkyne oligomerization mediated by rhodium complexes with a phosphinosulfonamido ligand and isolation and characterization of a rhodacyclopentadiene complex

Xue, Peng; Sung, Herman S.Y.; Williams, Ian D.; Jia, Guochen

doi:10.1016/j.jorganchem.2006.01.004

Cited by 19 publications

(13 citation statements)

References 77 publications

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“…The most significant difference concerns the angle P1–C2–C1, which is narrower in the rhodium complexes [ 5 : 112.44(17)°; 6 : 112.6(2)°] than in the lithium derivatives [ 1 : 120.18(9)°; 2 : 115.304(17)°], most likely to ensure better overlap between the phosphorus lone pair and the rhodium‐based orbitals. The resulting Rh–P bond of 2.3235(7) Å in [Rh(dbnP)(cod)] ( 5 ) is slightly longer than in [Rh(dbuP)(cod)] ( 6 ) [Rh–P 2.2719(7) Å] and the related amido–phosphine‐stabilized square‐planar rhodium complexes [Rh( P , N ‐Ph 2 PAr – )(cod)] [Rh–P 2.2534(3) Å; P , N ‐Ph 2 PAr – = P , N ‐diphenyl( o ‐ N ‐methylanilido)phosphine] and [Rh(Ph 2 PCH 2 CH 2 NTs)(cod)] [Rh–P 2.2606(6) Å; Ts = p ‐toluenesulfonyl] . The bond lengths towards and within the cod ligands in 5 and 6 agree well with the values reported for these known derivatives and therefore need no further discussion.…”

Section: Resultsmentioning

confidence: 99%

Lithium and Potassium Complexes with dbn‐ and dbu‐Based Enamido Phosphine Ligands: Syntheses and Applications

2017

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The phosphines 6-diphenylphosphino-1, 8-diazabicyclo[5.4.0]undec-7-ene (dbuPH) and 7-diphenylposphino-1,5-diazabicyclo[4.3.0]non-5-ene (dbnPH), containing amidine subunits, were successfully deprotonated by n-butyllithium or benzylpotassium. In the presence of Et 2 O or THF, the well-definedwas formed. These alkali-metal derivatives are useful precursors [a] Recently, we introduced two new monoanionic enamidophosphine ligands, based on phosphines with amidine subunits (see Scheme 1, D), and utilized them for the stabilization of large oligonuclear magnesium hydride species. [8] In this report, we investigate the synthesis of alkali-metal derivatives of these ligands and explore the utility of these compounds in organic synthesis and salt-metathesis reactions. Results and Discussion Lithium and Potassium DerivativesSalt-elimination reactions provide a simple tool to transfer anionic ligands to a desired metal center. Alkali-metal complexes, [a] Apparent unit cell derived from main reflections; presence of weak satellite reflections indicates unregarded modulation. [b] Flack parameter: 0.000(5).

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Section: Resultsmentioning

confidence: 99%

Lithium and Potassium Complexes with dbn‐ and dbu‐Based Enamido Phosphine Ligands: Syntheses and Applications

2017

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“…The CCCO moieties are alkynyl ketones (RCCCOR′), alkynyl esters (RCCCOOR′), alkynyl diesters (ROOCCCCOOR′), etc. The metal atoms of the metal compounds such as Mn, Re, Fe, Ru, Os, Rh, Ir, Ni, Pd and Pt are used for these cyclization reactions 84–113. In the CCCO moiety, the metal is coordinated at two coordination sites: the alkynyl π‐electron bond and the carbonyl oxygen atom.…”

Section: Synthesis Of Carbonyl Group‐containing Organometallic Intrammentioning

confidence: 99%

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

Omae¹

2010

Applied Organom Chemis

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Carbonyl group-containing organometallic intramolecular-coordination five-membered ring compounds are easily synthesized by the following five reaction methods: (1) cyclometalation, especially, orthometalation reactions; (2) the reactions of the moieties of an unsaturated carbon-carbon bond attached to a carbonyl group (C C-CO, C C-CO); (3) the reactions of an unsaturated carbon-carbon bond with carbon monoxide (C C and CO, C C and CO); (4) carbonylative ring expansion reactions; and (5) others. These compounds are very easily and regio-specifically synthesized with many kinds of metal compounds, including both transition metals and main group metals. Many of such the reactions are easily applied to organic syntheses.

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“…It involves the reaction of [{RhCl(CO) 2 } 2 ] with urea to form the coordinatively unsaturated monomeric intermediate A, [15] which undergoes oxidative coupling with alkynes to form rhodacyclopentadiene intermediate B, and subsequent insertion of CO and the formation of cyclopentadienone-coordinated rhodium intermediate C, followed by selective hydrogenation to afford 2 and/or 3. The rhodacyclopentadiene complex B from the reaction of rhodium complex with alkynes, [16] and cyclopentadienone-coordinated complex C [17] have been well studied. Furthermore, rhodium-catalyzed selective hydroge- nation of C-type compounds to 2-cyclopenten-1-one has been also reported.…”

Section: Resultsmentioning

confidence: 99%

Rhodium(I)‐Catalyzed Reductive Cyclocarbonylation of Internal Alkynes: Atom‐Economic Process for Synthesis of 2‐Cyclopenten‐1‐ones, 5‐Alkylidenefuran‐2(5 H)‐ones and Indan‐1‐ones

Huang¹,

Hua²

2009

Chemistry A European J

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The reductive cyclocarbonylation of internal alkynes with carbon monoxide catalyzed by [{RhCl(CO)(2)}(2)]/CO(NH(2))(2) in the presence of water has been investigated. Dialkyl alkynes underwent a reductive [2+2+1] cyclocarbonylation to afford selectively cis-2-cyclopenten-1-ones in high yields. In the cases of diarylacetylenes used, both trans-2-cyclopenten-1-ones and 5-alkylidenefuran-2(5 H)-ones were obtained, and the presence of electron-withdrawing group on the benzene ring enhanced the formation of 5-alkylidenefuran-2(5 H)-ones. On the other hand, ortho-substituted diarylacetylenes underwent a reductive [4+1] cyclocarbonylation to produce selectively indan-1-ones in good yields.

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Alkyne oligomerization mediated by rhodium complexes with a phosphinosulfonamido ligand and isolation and characterization of a rhodacyclopentadiene complex

Cited by 19 publications

References 77 publications

Lithium and Potassium Complexes with dbn‐ and dbu‐Based Enamido Phosphine Ligands: Syntheses and Applications

Lithium and Potassium Complexes with dbn‐ and dbu‐Based Enamido Phosphine Ligands: Syntheses and Applications

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

Rhodium(I)‐Catalyzed Reductive Cyclocarbonylation of Internal Alkynes: Atom‐Economic Process for Synthesis of 2‐Cyclopenten‐1‐ones, 5‐Alkylidenefuran‐2(5 H)‐ones and Indan‐1‐ones

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