Methyl–oxygen bond cleavage in hemilabile phosphine–ether ligand of ruthenium(II) complexes

Hsu, Sodio C. N.; Hu, Shih-Chieh; Wu, Zih-Shing; Chiang, Michael Y.; Hung, Min-Yuan

doi:10.1016/j.jorganchem.2009.01.032

Cited by 11 publications

(8 citation statements)

References 22 publications

(39 reference statements)

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“…43,44 While the coordination mode of ruthenium observed here in 4b is known, it is usually achieved by reacting a 2-methoxy-substituted phosphine with ruthenium(III) chloride. 45−47 Only a few examples are known where an arene displacement leads to this coordination motif. 44,48…”

Section: Resultsmentioning

confidence: 99%

Facile Arene Ligand Exchange in p-Cymene Ruthenium(II) Complexes of Tertiary P-Chiral Ferrocenyl Phosphines

2019

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Half-sandwich arene–metal complexes are commonly used for specific applications. Herein, we report facile arene ligand exchange reactions of two ruthenium(II) complexes of tertiary P-stereogenic ferrocenyl phosphines. By mild photochemical activation, the displacement of p-cymene and subsequent tethering by η6-coordination of the terminal phenyl ring of a biphenylyl-substituted ferrocenyl phosphine were enabled. Furthermore, the spontaneous p-cymene displacement in a 2-methoxyphenyl-containing ferrocenyl phosphine and ensuing coordination of the ligand as a P,O chelate were examined. For both reactions, theoretical calculations of the general course of the reaction confirmed the experimental findings. The ease of the controlled arene displacement reported here can offer new pathways for the synthesis and design of novel tailor-made catalysts.

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Section: Resultsmentioning

confidence: 99%

Facile Arene Ligand Exchange in p-Cymene Ruthenium(II) Complexes of Tertiary P-Chiral Ferrocenyl Phosphines

2019

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“…The very rapid displacement of the two -OMe groups from the ruthenium centre in 1 by CO suggests that the two chiral phosphinite ligands in this complex do indeed act as hemila-bile bidentate ligands with the methoxyl groups masking potentially vacant coordination sites at the metal centre. [29][30][31][32][33] On the basis of the similarity of the spectral properties of the closely related complexes 2-7, it is most likely that the phosphinite ligands in these compounds also act as hemilabile bidentate ligands. The labile donor bond formed between a hemilabile ligand and a metal can provide the metal with the capacity to readily accommodate incoming substrate molecules during catalysis.…”

Section: Syntheses Of the Ruthenium And Osmium Monophosphinite Comple...mentioning

confidence: 99%

“…In this arrangement the monophosphinites behave as classic hemilabile bidentate ligands with the methoxyl groups masking potentially vacant coordination sites at the metal centres. [29][30][31][32][33] In this paper we specifically report: (i) the synthesis of the four chiral monophosphinite compounds 1D-1,2; 6), OsCl 2 (D-P1) 2 (7), and RuCl 2 (CO) 2 (D-P1) 2 (8) through carbonylation of 1; (iii) the X-ray crystal structure determination of 1; and (iv) investigation of 1-7 as precatalysts for homogeneous asymmetric hydrogenation of the prochiral substrates acetophenone and 3-quinuclidinone.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions

Slade

Lensink²,

Falshaw³

et al. 2014

Dalton Trans.

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The monophosphinite ligands, 1D-1,2;5,6-di-O-cyclopentylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P1), 1D-1,2;5,6-di-O-isopropylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P2), 1D-1,2;5,6-di-O-cyclohexylidene-3-O-methyl-4-O-diphenylphosphino-chiro-inositol (D-P3), and 1D-1,2;5,6-di-O-cyclopentylidene-3-O-ethyl-4-O-diphenylphosphino-chiro-inositol (D-P4), can be conveniently prepared from the chiral natural products 1D-pinitol or 1D-chiro-inositol. On treatment of toluene solutions of RuCl2(PPh3)3 with two mole equivalents of the ligands D-PY (Y = 1-4) the complexes RuCl2(D-P1)2 (1), RuCl2(D-P2)2 (4), RuCl2(D-P3)2 (5), or RuCl2(D-P4)2 (6), respectively, are formed. Similarly, treatment of OsCl2(PPh3)3 with D-P1 gives OsCl2(D-P1)2 (7). The single crystal X-ray structure determination of 1 reveals that each D-P1 ligand coordinates to ruthenium through phosphorus and the oxygen atom of the methoxyl group. Treatment of 1 with excess LiBr or LiI results in metathesis of the chloride ligands and RuBr2(D-P1)2 (2) or RuI2(D-P1)2 (3), respectively, are formed. Exposure of a solution of 1 to carbon monoxide results in the very rapid formation of RuCl2(CO)2(D-P1)2 (8), thereby demonstrating the ease with which the oxygen donors are displaced from the metal and hence the hemilabile nature of the two bidentate D-P1 ligands in 1. Preliminary studies indicate that 1-7 act as catalysts for the asymmetric hydrogenation reactions of acetophenone and 3-quinuclidinone to give the corresponding alcohols in generally high conversions but low enantiomeric excesses.

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“…The OMe groups are observed in the 1 H NMR spectrum at δ 3.05 and δ 3.18 as sharp singlets, shifted upfield from the free ligand, suggesting that they do not interact strongly with the metal center, as OMe signals have been shown to shift downfield on coordination. [20] Addition of the corresponding acyl chloride 4 c to 3 a resulted in a structurally characterized complex [Rh( 2 a )(Cl)(κ,σ-1,2-SMe(CO)C 6 H 4 )][BAr F 4 ] ( 11 ; Figure 1 B). Although this shows a different relative orientation of ligands compared with that determined spectroscopically for 10 (and by inference 8 ), in which, most likely due to the π-donor chloride, the acyl group is trans to the vacant site, it also shows that the OMe group does not approach the metal center [Rh1–O2 3.682 Å].…”

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confidence: 99%

Well‐Defined and Robust Rhodium Catalysts for the Hydroacylation of Terminal and Internal Alkenes

et al. 2015

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Methyl–oxygen bond cleavage in hemilabile phosphine–ether ligand of ruthenium(II) complexes

Cited by 11 publications

References 22 publications

Facile Arene Ligand Exchange in p-Cymene Ruthenium(II) Complexes of Tertiary P-Chiral Ferrocenyl Phosphines

Facile Arene Ligand Exchange in p-Cymene Ruthenium(II) Complexes of Tertiary P-Chiral Ferrocenyl Phosphines

Ruthenium and osmium complexes of hemilabile chiral monophosphinite ligands derived from 1D-pinitol or 1D-chiro-inositol as catalysts for asymmetric hydrogenation reactions

Well‐Defined and Robust Rhodium Catalysts for the Hydroacylation of Terminal and Internal Alkenes

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