Hydrido(phosphine)ruthenate complexes and their role in the catalytic hydrogenation of arenes

Fordyce, William; Wilczynski, Robert; Halpern, Jack

doi:10.1016/0022-328x(85)80343-0

Cited by 28 publications

(13 citation statements)

References 21 publications

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“…3.5, 1.5, and 1 h, respectively (Scheme ). Complex 1 gave a mixture of fac-[Ru(PPh 3 ) 2 (C 6 H 4 PPh 2 )H 2 ][Li(THF) n ] ( 7-Li ) , and fac-[Ru(PPh 3 ) 3 H 3 ][Li(THF) 3 ] ( 8-Li ), − ,, which, over 24 h, converted completely to 8-Li . The reaction of 2 with H 2 proceeded with dissociation of the crown ligand from Li to also yield a mixture of 7-Li and 8-Li , whereas 3 yielded [Ru(PPh 3 ) 3 H 3 ][MgMe(THF) n ] ( 8-Mg ) as the major product, without formation of any significant quantities of 7-Mg (ESI).…”

Section: Resultsmentioning

confidence: 99%

Zn-Promoted C–H Reductive Elimination and H₂ Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

et al. 2020

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Reaction of [Ru(PPh 3 ) 3 HCl] with LiCH 2 TMS, MgMe 2 , and ZnMe 2 proceeds with chloride abstraction and alkane elimination to form the biscyclometalated derivatives [Ru(PPh 3 )(C 6 H 4 PPh 2 ) 2 H][M′] where [M′] = [Li-(THF) 2 ] + (1), [MgMe(THF) 2 ] + (3), and [ZnMe] + (4), respectively. In the presence of 12-crown-4, the reaction with LiCH 2 TMS yields [Ru(PPh 3 )(C 6 H 4 PPh 2 ) 2 H][Li(12crown-4) 2 ] (2). These four complexes demonstrate increasing interaction between M′ and the hydride ligand in the [Ru(PPh 3 )(C 6 H 4 PPh 2 ) 2 H] − anion following the trend 2 (no interaction) < 1 < 3 < 4 both in the solid-state and solution. Zn species 4 is present as three isomers in solution including square-pyramidal [Ru-(PPh 3 ) 2 (C 6 H 4 PPh 2 )(ZnMe)] (5), that is formed via C−H reductive elimination and features unsaturated Ru and Zn centers and an axial Z-type [ZnMe] + ligand. A [ZnMe] + adduct of 5, [Ru(PPh 3 ) 2 (C 6 H 4 PPh 2 )(ZnMe) 2 ][BAr F 4 ] ( 6) can be trapped and structurally characterized. 4 reacts with H 2 at −40 °C to form [Ru(PPh 3 ) 3 (H) 3 (ZnMe)], 8-Zn, and contrasts the analogous reactions of 1, 2, and 3 that all require heating to 60 °C. This marked difference in reactivity reflects the ability of Zn to promote a rate-limiting C−H reductive elimination step, and calculations attribute this to a significant stabilization of 5 via Ru → Zn donation. 4 therefore acts as a latent source of 5 and this operational "dual unsaturation" highlights the ability of Zn to promote reductive elimination in these heterobimetallic systems. Calculations also highlight the ability of the heterobimetallic systems to stabilize developing protic character of the transferring hydrogen in the rate-limiting C−H reductive elimination transition states.

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Section: Resultsmentioning

confidence: 99%

Zn-Promoted C–H Reductive Elimination and H₂ Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

et al. 2020

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“…The dihydride-dihydrogen 42 is deprotonated by c -C 6 H 11 O – to reach an equilibrium with the anionic trihydride [RuH 3 (PPh 3 ) 3 ] − ( 47 ) and cyclohexanol ( K eq ≈ 0.13 at ambient temperature in THF) . This anion is conveniently prepared by means of reaction of [RuH 2 (PPh 3 ) 2 {κ 2 - P , C -PPh 2 (C 6 H 4 )}] − ( 48 ) with H 2 (1 atm). , After adding a slight excess of 18-crown-6-ether to its THF solutions, single crystals of the [K(C 12 H 24 O 6 )] + -salt of 47 suitable for X-ray diffraction analysis were obtained. The structure revealed a fac -disposition of both hydride and phosphine ligands in an octahedral environment .…”

Section: Rutheniummentioning

confidence: 99%

“…100 This anion is conveniently prepared by means of reaction of [RuH 2 (PPh 3 ) 2 {κ 2 -P,C-PPh 2 (C 6 H 4 )}] − (48) with H 2 (1 atm). 101,102 After adding a slight excess of 18crown-6-ether to its THF solutions, single crystals of the [K(C 12 H 24 O 6 )] + -salt of 47 suitable for X-ray diffraction analysis were obtained. The structure revealed a fac-disposition of both hydride and phosphine ligands in an octahedral environment.…”

Section: Ruthenium 21 Phosphine Complexesmentioning

confidence: 99%

Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions

2016

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The preparation, structure, dynamic behavior in solution, and reactivity of polyhydride complexes of platinum group metals, described during the last three decades, are contextualized from both organometallic and coordination chemistry points of view. These compounds, which contain dihydrogen, elongated dihydrogen, compressed dihydride, and classical dihydride ligands promote the activation of B-H, C-H, Si-H, N-H, O-H, C-C, C-N, and C-F, among other σ-bonds. In this review, it is shown that, unlike other more mature areas, the chemistry of polyhydrides offers new exciting conceptual challenges and at the same time the possibility of interacting with other fields including the conversion and storage of regenerative energy, organic synthetic chemistry, drug design, and material science. This wide range of possible interactions foresees promising advances in the near future.

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“…Anionic hydride complexes with few or no carbonyl ligands are required for our studies to avoid the formation of conventional MCO−HN hydrogen bonds. There are only a few examples of hydridophosphinemetalate complexes which do not contain carbonyl ligands; examples include fac -[RuH 3 (PPh 3 ) 3 ] - , , [WH 5 (PMe 3 ) 3 ] - , [RuH 2 (C 6 H 4 PPh 2 )(PPh 3 ) 2 ] - , , [OsH 5 (P i Pr 3 ) 2 ] - , [OsH 3 (PMe 2 Ph) 3 ] - , and [RuH 5 (PPh 3 ) 2 ] - . , The most common method of preparation of such complexes is the deprotonation of neutral metal polyhydrides by use of a strong base such as KH or BuLi (eq 1) …”

Section: Introductionmentioning

confidence: 99%

New Polyhydride Anions and Proton-Hydride Hydrogen Bonding in Their Ion Pairs. X-ray Crystal Structure Determinations of Q[mer-Os(H)₃(CO)(PⁱPr₃)₂], Q = [K(18-crown-6)] and Q = [K(1-aza-18-crown-6)]

1998

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The transition metal halides Re(H2)Br2(NO)(PiPr3)2 and MHCl(CO)(PiPr3)2, M = Ru, Os afforded the hydrido(tertiary phosphine)metalates [ReH3(NO)(PiPr3)2]- and [MH3(CO)(PiPr3)2]-, M Ru, Os in reactions with KH in the presence of crown ethers (2.2.2-crypt, 18-crown-6, 1-aza-18-crown-6) under H2. The anionic hydrides [RuH3(PPh3)3]- and [MH5(PiPr3)2]-, M = Ru, Os were also efficiently prepared by this method. The trihydrides [K(18-crown-6)][OsH3(CO)(PiPr3)2] and [K(1-aza-18-crown-6)][OsH3(CO)(PiPr3)2] were characterized by single-crystal X-ray diffraction and possess the mer structure with two trans hydride ligands. Unlike the former structure, the latter is chain polymeric via CO···K+ links and NH···HOs hydrogen bonds; this is the first one-dimensional network to be held together by proton−hydride bonding. The [K(1-aza-18-crown-6)]+ N−H IR band shift (Δν) indicates the increasing strength of hydrogen bonding with the following hydrides: [ReH3(NO)(PiPr3)2]- (102 cm-1) < [OsH3(CO)(PiPr3)2]- (116 cm-1) < [RuH3(CO)(PiPr3)2]- (136 cm-1). The order of acidity of the conjugate acid forms follows a different trend: Os(H2)(H)2(CO)(PiPr3)2 > Re(H)4(NO)(PiPr3)2 > Ru(H2)(H)2(CO)(PiPr3)2. The crypt-containing cations interact weakly with the anions in [K(2.2.2-crypt)][OsH3(CO)(PiPr3)2] and [K(2.2.2-crypt)][RuH3(CO)(PiPr3)2] in toluene or tetrahydrofuran (THF). This results in the formation of only the mer isomers. Substantial ion-pairing between [K(18-crown-6)]+ and the trihydrides results in the stabilization of the fac isomers to a greater degree in toluene than in polar THF. Use of [K(1-aza-18-crown-6)]+ results in even greater stabilization of the fac isomers both in THF and toluene. Nuclear Overhauser effect (NOE) experiments reveal that NH···HM hydrogen bonds cause tighter ion pairing in this case.

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Hydrido(phosphine)ruthenate complexes and their role in the catalytic hydrogenation of arenes

Cited by 28 publications

References 21 publications

Zn-Promoted C–H Reductive Elimination and H₂ Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

Zn-Promoted C–H Reductive Elimination and H₂ Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions

New Polyhydride Anions and Proton-Hydride Hydrogen Bonding in Their Ion Pairs. X-ray Crystal Structure Determinations of Q[mer-Os(H)₃(CO)(PⁱPr₃)₂], Q = [K(18-crown-6)] and Q = [K(1-aza-18-crown-6)]

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Hydrido(phosphine)ruthenate complexes and their role in the catalytic hydrogenation of arenes

Cited by 28 publications

References 21 publications

Zn-Promoted C–H Reductive Elimination and H2 Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

Zn-Promoted C–H Reductive Elimination and H2 Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions

New Polyhydride Anions and Proton-Hydride Hydrogen Bonding in Their Ion Pairs. X-ray Crystal Structure Determinations of Q[mer-Os(H)3(CO)(PiPr3)2], Q = [K(18-crown-6)] and Q = [K(1-aza-18-crown-6)]

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Zn-Promoted C–H Reductive Elimination and H₂ Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

Zn-Promoted C–H Reductive Elimination and H₂ Activation via a Dual Unsaturated Heterobimetallic Ru–Zn Intermediate

New Polyhydride Anions and Proton-Hydride Hydrogen Bonding in Their Ion Pairs. X-ray Crystal Structure Determinations of Q[mer-Os(H)₃(CO)(PⁱPr₃)₂], Q = [K(18-crown-6)] and Q = [K(1-aza-18-crown-6)]