Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl2(PPh3)(Ppy3) (py = 2-pyridyl)

Schutte, Richard P.; Rettig, Steven J.; James, Brian R.

doi:10.1139/v96-235

Cited by 15 publications

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References 22 publications

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“…When the sample was then heated, the spectrum changed again, showing two singlets as well as the singlet for free PPh 3 . The complex associated with the two singlets is RuCl 2 (PPh 3 )( N,N ‘ ,N ‘‘-P(py) 3 ) and has been described elsewhere …”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF₆(PP = (PPh₃)₂, Ph₂P(CH₂)₄PPh₂; L = P(py)₃, PPh(py)₂, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines

et al. 1997

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The complexes [RuCl(PPh(3))(2)(P,N,N'-PPh(3-)(x)()(py)(x)())]PF(6) (x = 2, 1b; 3, 1c; py = 2-pyridyl) were isolated from the reaction of RuCl(2)(PPh(3))(3) with 1 equiv of PPh(3-)(x)()(py)(x)() and NH(4)PF(6) in acetone. Crystals of 1b (C(52)H(43)ClF(6)N(2)P(4)Ru) are monoclinic, a = 17.795(2), b = 11.375(4), and c = 23.343(2) Å, beta = 97.012(8) degrees, Z = 4, space group P2(1)/c; those for 1c (C(51)H(42)ClF(6)N(3)P(4)Ru) are monoclinic, a = 17.812(1), b = 11.353(2), and c = 23.391(1) Å, beta = 97.738(5) degrees, Z = 4, space group P2(1)/c. The isomorphous structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.036 and 0.033 (R(w) = 0.035 and 0.031) for 7690 and 8121 reflections with I >/= 3sigma(I), respectively. The P,N,N'-coordination mode for 2-pyridylphosphines is previously unreported. The P,N-coordinated complexes cis-RuCl(2)(dppb)(PPh(3-)(x)()(py)(x)()) (x = 1-3; dppb = Ph(2)P(CH(2))(4)PPh(2)) were made by isomerization of the corresponding trans-dichloro isomers, which are themselves synthesized from RuCl(2)(dppb)(PPh(3)). The cis complexes in CHCl(3) or CH(2)Cl(2) dissociate chloride reversibly with formation of P,N,N'-coordinated PPh(3-)(x)()(py)(x)() species, which were isolated as [RuCl(dppb)(PPh(3-)(x)()(py)(x)())]PF(6) (x = 2, 3). Reactions of CO with the species containing the strained P,N,N'-coordination mode lead to displacement of a coordinated pyridyl and formation of the P,N-coordinated complexes [RuCl(CO)(PP)(PPh(3-)(x)()(py)(x)())]PF(6) (PP = (PPh(3))(2), x = 2, 3; and PP = dppb, x = 2, 3). The CO reactions are partially reversible. Solution structures of the complexes were determined by NMR, IR, and UV-visible spectroscopies and conductivity.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF₆(PP = (PPh₃)₂, Ph₂P(CH₂)₄PPh₂; L = P(py)₃, PPh(py)₂, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines

et al. 1997

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“…The coordination chemistry of Py 3 PO is relatively unexplored and complexes are oen accessed by post-functionalization of the corresponding tris(2-pyridyl)phosphine complex. [30][31][32][33][34] A new route to the free phosphine oxide ligand was recently reported by Tromov and co-workers. 29 Instead of a low temperature lithiation strategy, red phosphorous and 2-bromopyridine were heated under strongly basic conditions.…”

Section: Synthesis and Characterization Of Ru Complexesmentioning

confidence: 99%

Rapid water oxidation electrocatalysis by a ruthenium complex of the tripodal ligand tris(2-pyridyl)phosphine oxide

Walden

Miller

2015

Chem. Sci.

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Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions

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Meyer

Krummenacher

et al. 2008

Chemistry A European J

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Reactions of HC(Me2pz)3 with Grignard reagents, dialkyl magnesium compounds and dimethylzinc are reported, together with a DFT study on some of the aspects of this chemistry. Reactions of HC(Me2pz)3 with MeMgX (X=Cl or Br) gave the half-sandwich zwitterionic compounds [Mg((Me)Tpmd)X] (X=Cl (2) or Br (3); (Me)Tpmd(-)=[C(Me2pz)3](-)). Addition of HCl to 2 gave the structurally characterised half-sandwich compound [Mg{HC(Me2pz)3}Cl2(thf)] (4). The zwitterionic sandwich compound [Mg(MeTpmd)2] (5) formed in low yields in the reaction of MeMgX with HC(Me2pz)3 but was readily prepared from HC(Me2pz)3 and either MgnBu2 or MgPh2. The structurally characterised compound 5 contains two "naked" sp3-hybridised carbanions fully separated from the dicationic metal centre. Only by using MgPh2 as starting material could the half-sandwich compound [Mg(MeTpmd)Ph(thf)] (6) be isolated. The zwitterionic sandwich compound 5 reacted with HOTf (OTf(-)=[O3SCF3](-)) to form the dication [Mg{HC(Me2pz)3}2]2+ (7(2+)), which was structurally characterised. Pulsed field gradient spin-echo (PGSE) diffusion NMR spectroscopy revealed both compounds to be intact in solution. In contrast to the magnesium counterparts, HC(Me2pz)3 reacted only slowly with ZnMe2 (and not at all with ZnPh2) to form the half-sandwich zwitterion [Zn(MeTpmd)Me] (8), which contains a cationic methylzinc moiety separated from a single sp3-hybridised carbanion. Density functional calculations on the zwitterions [M(MeTpmd)Me] and [M(MeTpmd)2] (M=Mg, Zn) revealed that the HOMO in each case is a (Me)Tpmd-based carbanion lone pair. The kappa 1C isomers of [M(MeTpmd)Me] were calculated to be considerably less stable than their kappa 3N-bound counterparts, with the largest gain in energy for Mg due to the greater ease of electron transfer from metal to the (Me)Tpmd apical carbon atom on formation of the zwitterion. Moreover, the computed M-C bond dissociation enthalpies of the kappa 1C isomers of [M(MeTpmd)Me] are considerably higher than expected by simple extrapolation from the corresponding computed H-C bond dissociation enthalpy.

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Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)

Abstract: Reaction of RuCI,(PPh,), with Ppy, (py = 2-pyridyl) in benzene produced the N,N',Nff-Ppy, complex RuCI,(PPh,)(Ppy,) 1. Crystals of RuC1,(PPh3)(Ppy3).2CH,C12 (C,,H,,C16N,P,Ru)

Cited by 15 publications

References 22 publications

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF₆(PP = (PPh₃)₂, Ph₂P(CH₂)₄PPh₂; L = P(py)₃, PPh(py)₂, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF₆(PP = (PPh₃)₂, Ph₂P(CH₂)₄PPh₂; L = P(py)₃, PPh(py)₂, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines

Rapid water oxidation electrocatalysis by a ruthenium complex of the tripodal ligand tris(2-pyridyl)phosphine oxide

Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions

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Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl2(PPh3)(Ppy3) (py = 2-pyridyl)

Abstract: Reaction of RuCI,(PPh,), with Ppy, (py = 2-pyridyl) in benzene produced the N,N',Nff-Ppy, complex RuCI,(PPh,)(Ppy,) 1. Crystals of RuC1,(PPh3)(Ppy3).2CH,C12 (C,,H,,C16N,P,Ru)

Cited by 15 publications

References 22 publications

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF6(PP = (PPh3)2, Ph2P(CH2)4PPh2; L = P(py)3, PPh(py)2, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF6(PP = (PPh3)2, Ph2P(CH2)4PPh2; L = P(py)3, PPh(py)2, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines

Rapid water oxidation electrocatalysis by a ruthenium complex of the tripodal ligand tris(2-pyridyl)phosphine oxide

Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions

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Synthesis, characterization, and reactivity of a ruthenium(II)N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl₂(PPh₃)(Ppy₃) (py = 2-pyridyl)

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF₆(PP = (PPh₃)₂, Ph₂P(CH₂)₄PPh₂; L = P(py)₃, PPh(py)₂, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF₆(PP = (PPh₃)₂, Ph₂P(CH₂)₄PPh₂; L = P(py)₃, PPh(py)₂, py = 2-pyridyl). The “Missing”P,N,N‘-Coordination Mode for 2-Pyridylphosphines