511. Hydrido-complexes of ruthenium(II) and osmium(II)

Chatt, J.; Hayter, R. G.

doi:10.1039/jr9610002605

Cited by 61 publications

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“…These were assigned to the hydride fluoride complex [Ru(IEt 2 -Me 2 ) 2 (PPh 3 ) 2 HF] (2) and the pentafluorophenyl complex [Ru (IEt 2 Me 2 ) 2 (PPh 3 )(C 6 F 5 )H] (3) respectively (Scheme 2). 19 20 presumably results from the presence of a trans-labilising hydride ligand. C-H activation proved to be reversible.…”

Section: Resultsmentioning

confidence: 99%

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Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (IEt₂Me₂= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

et al. 2015

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The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H2] (; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] () and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (). The formation of resulted from C-H activation of C6F5H (formed from C6F6via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] () was isolated. A more efficient route to involved treatment of with 0.33 eq. of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3](-) salt () of the known cation [Ru(IEt2Me2)2(PPh3)2H](+). Under catalytic conditions, proved to be an active precursor for hydrodefluorination, converting C6F6 to a mixture of tri, di and monofluorobenzenes (TON = 37) at 363 K with 10 mol% and Et3SiH as the reductant.

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Section: Resultsmentioning

confidence: 99%

“…The 19 F NMR spectrum showed a broad fluoride resonance at δ −354 in both THF-d 8 and toluene-d 8 at room temperature, although the doublet hydride splitting of ca. The IEt 2 Me 2 signals were broad and overlapping, but resolved upon cooling to 228 K into eight sets of N-CH 2 and four sets N-CH 2 CH 3 signals respectively.…”

Section: Resultsmentioning

confidence: 99%

Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (IEt₂Me₂= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

et al. 2015

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“…The title compound was prepared by dissolving cisOsC12(dppe)2 [(2); prepared according to the method of Chatt & Hayter (1961)] and NaPF6 in a mixture of tetrahydrofuran and CH2C12. The reaction mixture was stirred at room temperature for 48 h resulting in a dark brown solution which was evaporated to dryness and redissolved in CH2C12.…”

Section: Methodsmentioning

confidence: 99%

Bis[1,2-bis(diphenylphosphino)ethane-P,P']chloroosmium(II) Hexafluorophosphate Dichloromethane Solvate

Lough¹,

Morris²,

Schlaf³

1996

Acta Crystallogr C

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The cation molecule of the title compound, [OsC1-(C26H24P2)2]PF6.1.5CH2C12, has a distorted trigonalbipyramidal structure. Despite strong steric repulsion between the PPh2 groups, the Os--P bonds in the equatorial plane are short [2.2416(12) and 2.2587(13)A] and the P---OsmP angle is only 94.24 (5) °. CommentThe title compound, (1), was synthesized in order to provide the starting material in the preparation of the dihydrogen complex trans-[Os(H2)Cl(dppe)2]PF6, (3) [where dppe is 1,2-bis(diphenylphosphino)ethane; see scheme below]. The X-ray and neutron diffraction studies of (3) are discussed elsewhere (Maltby et al., 1996). An X-ray study of the five-coordinate compound

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“…We find that all three steps of reaction [3] are necessary. The reaction of lithium aluminum hydride with cis-dichlorobis(diphosphine)osmium(II) compounds is known to produce the corresponding dihydrido and trans-hydridochloro complexes (28,30). However, addition of ethanol following the reaction often does not completely cleave aluminum species associated with the osmium centre.…”

Section: Synthesis Of the Precursor Complexesmentioning

confidence: 99%

“…cis-P-0sC12L, as a light yellow powder, was characterized by elemental analysis, FAB MS, and 3 1~ NMR, for which the ANQY spin pattern is very distinctive (Table 1 and see below). A mixture of isomers, trans-OsH(Cl)L, is produced in reaction [3], which is analogous to the one used to prepare trans-OsHCl(depe)2 (28,29 Fig. 3 for the numbering THF-d8 -13.7 dp" 20.6 THF "p = pentet, ac = acetone.…”

Section: Synthesis Of the Precursor Complexesmentioning

confidence: 99%

New dihydrogen complexes: the synthesis and spectroscopic properties of iron(II), ruthenium(II), and osmium(II) complexes containing the meso-tetraphos-1 ligand

Bautista¹,

Earl²,

Maltby³

et al. 1994

Can. J. Chem.

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Can. J. Chem. 72,547 (1994). The synthesis and properties of dihydrogen complexes trans-[MH(H2)L]+, M = Fe, Ru, Os, which contain the ligand mesotetraphos-1, S,R-Ph2PCH2CH2P(Ph)CH2CH2P(Ph)CH2CH2PPh2 (L) are described. There are interesting possibilities of isomerism in such trans complexes because the axial binding sites at the metal are different, one being surrounded by four phenyl groups and the other by two phenyl groups. The osmium complex is prepared in an unusual reaction of ci.~-p-Os(Cl)~L with HI, (1 atm) and NaBPh4 (1 mol) in THF or by the reaction of trans-OsH(C1)L with NaBPh4 and H2. The iron and ruthenium complexes were made by a reaction of HBF4 with complexes t r a n~-M ( H )~L that have inequivalent trans hydrides. The ruthenium complex was also prepared starting from isomers of t r a n s -R U H ( C~) L .~T~~ H-H distance in the rapidly spinning dihydrogen ligand has been calculated from Tl(min) data to be 0. [Traduit par la rtdaction]

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511. Hydrido-complexes of ruthenium(II) and osmium(II)

Cited by 61 publications

References 0 publications

Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (IEt₂Me₂= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (IEt₂Me₂= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

Bis[1,2-bis(diphenylphosphino)ethane-P,P']chloroosmium(II) Hexafluorophosphate Dichloromethane Solvate

New dihydrogen complexes: the synthesis and spectroscopic properties of iron(II), ruthenium(II), and osmium(II) complexes containing the meso-tetraphos-1 ligand

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511. Hydrido-complexes of ruthenium(II) and osmium(II)

Cited by 61 publications

References 0 publications

Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt2Me2)2(PPh3)2H2] (IEt2Me2= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt2Me2)2(PPh3)2H2] (IEt2Me2= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

Bis[1,2-bis(diphenylphosphino)ethane-P,P']chloroosmium(II) Hexafluorophosphate Dichloromethane Solvate

New dihydrogen complexes: the synthesis and spectroscopic properties of iron(II), ruthenium(II), and osmium(II) complexes containing the meso-tetraphos-1 ligand

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Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (IEt₂Me₂= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (IEt₂Me₂= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)