Hydride and borohydride derivatives of (pentamethylcyclopentadienyl)(tertiary phosphine)ruthenium

Suzuki, Hiroharu; Lee, Dong Hwan; Oshima, Noriaki; Moro‐oka, Yoshihiko

doi:10.1021/om00150a032

Cited by 61 publications

(49 citation statements)

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“…The Ru-H-B angles are acute [90 (2) and 97(2) • ], and coupled with the short Ru-B distance, this might implicate a structure with both r-boryl and hydride ligands. However, the B-Ru-H angles (36-38 36 This bidentate bonding mode is also similar to that reported for the spectroscopically characterised complexes [Cp*Ru(PR 3 )(g 2 -BH 4 )] (R = e.g., Me, PPh 3 ) 37 and those observed previously in the crystallographically characterised rhodium complexes of H 3 B•dppm: [(dppm•BH 3 )-nido-RhSB 9 H 10 ] 10 and [(cod)Rh(dppm•BH 3 )][PF 6 ]. 12 The Ru centre in 4 is formally 18-electron, although structurally the complex is more closely related to the 16-electron [Cp*Ru(PMe i Pr 2 ) 2 ] + complexes that also have C s symmetry.…”

Section: Methodssupporting

confidence: 80%

Transition metal complexes of the chelating phosphine borane ligand Ph₂PCH₂Ph₂P·BH₃

et al. 2004

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Chromium and ruthenium complexes of the chelating phosphine borane H(3)B.dppm are reported. Addition of H(3)B.dppm to [Cr(CO)(4)(nbd)](nbd = norbornadiene) affords [Cr(CO)(4)(eta1-H(3)B.dppm)] in which the borane is linked to the metal through a single B-H-Cr interaction. Addition of H(3)B.dppm to [CpRu(PR(3))(NCMe)(2)](+)(Cp =eta5)-C(5)H(5)) results in [CpRu(PR(3))(eta1-H(3)B.dppm)][PF(6)](R = Me, OMe) which also show a single B-H-Ru interaction. Reaction with [CpRu(NCMe)(3)](+) only resulted in a mixture of products. In contrast, with [Cp*Ru(NCMe)(3)](+)(Cp*=eta5)-C(5)Me(5)) a single product is isolated in high yield: [Cp*Ru(eta2-H(3)B.dppm)][PF(6)]. This complex shows two B-H-Ru interactions. Reaction with L = PMe(3) or CO breaks one of these and the complexes [Cp*Ru(L)(eta1-H(3)B.dppm)][PF(6)] are formed in good yield. With L = MeCN an equilibrium is established between [Cp*Ru(eta2-H(3)B.dppm)][PF(6)] and the acetonitrile adduct. [Cp*Ru (eta2-H(3)B.dppm)][PF(6)] can be considered as being "operationally unsaturated", effectively acting as a source of 16-electron [Cp*Ru (eta1-H(3)B.dppm)][PF(6)]. All the new compounds (apart from the CO and MeCN adducts) have been characterised by X-ray crystallography. The solid-state structure of H(3)B.dppm is also reported.

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Section: Methodssupporting

confidence: 80%

Transition metal complexes of the chelating phosphine borane ligand Ph₂PCH₂Ph₂P·BH₃

et al. 2004

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“…IPrCuCl was prepared by the reaction of free IPr with CuCl in THF; purification followed literature procedures . Cp*( i Pr 2 MeP)RuCl , and Cp*( i Pr 2 MeP)RuH 3 , were prepared by literature procedures.…”

Section: Methodsmentioning

confidence: 99%

An Anionic Ruthenium Dihydride [Cp*(ⁱPr₂MeP)RuH₂]⁻ and Its Conversion to Heterobimetallic Ru(μ-H)₂M (M = Ir or Cu) Complexes

et al. 2019

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A novel dihydridoruthenate, [(solv)Na][Cp*-( i Pr 2 MeP)RuH 2 ] (2; solv = THF or OEt 2 ), was synthesized from Cp*( i Pr 2 MeP)RuCl (1) and sodium triethylborohydride. Compound 2 was used to generate "Cp*( i Pr 2 MeP)RuH" equivalents by salt metathesis with 1, which resonance Raman spectroscopy indicates is a mixture of the terminal dinitrogen complex, Cp*( i Pr 2 MeP)RuH(N 2 ) (4), and diastereomers of the bridging dinitrogen complex [Cp*( i Pr 2 MeP)RuH] 2 (μ-N 2 ) (meso, 5, and a pair of enantiomers, 6). Compound 2 also reacted with the late transition metal chloride complexes [(COD)IrCl] 2 and (IPr)CuCl [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] to form hydride-bridged heterobimetallic complexes Cp*( i Pr 2 MeP)Ru(μ-H) 2 Ir(COD) (7) and Cp*( i Pr 2 MeP)Ru(μ-H) 2 Cu(IPr) (8), respectively, that feature weakened Ru−H interactions relative to those of 2.

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“…The magnitudes of J AB are reflected in the chemical shift of the ruthenium-bound protons at room temperature. Suzuki et al 8 noted that the shift was 'consistent with the electronic parameters of the PR 3 ligand according to Tolman' for the generic [Cp*RuH 3 (PR 3 )] complexes. The d values of ca.…”

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confidence: 66%

“…The dependence of QMEC on phosphine basicity has been firmly established, most notably in the series of complexes [Cp*RuH 3 (PR 3 )] and [Cp*IrH 3 (PR 3 )] + . [8][9][10] Strongly p-accepting phosphines assist QMEC by lowering the barrier to interconversion (DG { in Fig. 1), ostensibly by stablilising a MH(g 2 -H 2 ) component, resulting in high values for J AB ; e.g.…”

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confidence: 99%

Ruthenium trihydrides with N-heterocyclic carbene ligands: effects on quantum mechanical exchange coupling

et al. 2005

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Hydride and borohydride derivatives of (pentamethylcyclopentadienyl)(tertiary phosphine)ruthenium

Cited by 61 publications

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Transition metal complexes of the chelating phosphine borane ligand Ph₂PCH₂Ph₂P·BH₃

Transition metal complexes of the chelating phosphine borane ligand Ph₂PCH₂Ph₂P·BH₃

An Anionic Ruthenium Dihydride [Cp*(ⁱPr₂MeP)RuH₂]⁻ and Its Conversion to Heterobimetallic Ru(μ-H)₂M (M = Ir or Cu) Complexes

Ruthenium trihydrides with N-heterocyclic carbene ligands: effects on quantum mechanical exchange coupling

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Hydride and borohydride derivatives of (pentamethylcyclopentadienyl)(tertiary phosphine)ruthenium

Cited by 61 publications

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Transition metal complexes of the chelating phosphine borane ligand Ph2PCH2Ph2P·BH3

Transition metal complexes of the chelating phosphine borane ligand Ph2PCH2Ph2P·BH3

An Anionic Ruthenium Dihydride [Cp*(iPr2MeP)RuH2]− and Its Conversion to Heterobimetallic Ru(μ-H)2M (M = Ir or Cu) Complexes

Ruthenium trihydrides with N-heterocyclic carbene ligands: effects on quantum mechanical exchange coupling

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Transition metal complexes of the chelating phosphine borane ligand Ph₂PCH₂Ph₂P·BH₃

Transition metal complexes of the chelating phosphine borane ligand Ph₂PCH₂Ph₂P·BH₃

An Anionic Ruthenium Dihydride [Cp*(ⁱPr₂MeP)RuH₂]⁻ and Its Conversion to Heterobimetallic Ru(μ-H)₂M (M = Ir or Cu) Complexes