Dicarbonylbis(triphenylphosphine)nickel(0): a redetermination at 90 K

Moncóľ, Ján; Gembický, Milan; Coppens, P.

doi:10.1107/s1600536804024377

Cited by 3 publications

(2 citation statements)

References 6 publications

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“…In the solid state, the benzene rings in 9i are mutually twisted by 51.5(1)°, presumably to avoid possible spatial interactions of the hydrogen atoms in the ortho positions. This feature and the CO bond length (1.234(3) Å) are similar to those observed for unsubstituted benzophenone …”

Section: Resultssupporting

confidence: 80%

Synthesis, Structural Characterization, and Catalytic Evaluation of Phosphinoferrocene Ligands Bearing Extended Urea-Amide Substituents

Solařová¹,

Cı́sařová²,

Štěpnička³

2014

Organometallics

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New phosphinoferrocene ligands bearing extended polar amidourea pendants with the general formula Ph 2 PfcCONHCH 2 CH 2 NHCONR 2 (1; R 2 = H 2 (b), H/Et (c), Me 2 (d), H/Ph (e)) and their model bis-amide Ph 2 PfcCONHCH 2 CH 2 NHCOCH 3 (1a) were prepared in good yields by amidation of 1′-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) with the appropriate amines in the presence of peptide coupling reagents. These ferrocene-based phosphinoureas were further employed as ligands in palladium(II) complexes with η 3 -allyl and NCchelating supporting ligands: viz., [). Both the free ligands and their Pd(II) complexes were characterized by spectroscopic methods (multinuclear NMR, IR, and MS) and by elemental analysis. The molecular structures of 1b•CH 3 OH, 1c, 5b,c, 6a, and two additional model complexes, [PdCl(η 3 -C 3 H 5 )(Hdpf-κP)] (5f) and [PdCl(η 3 -C 3 H 5 )(Ph 2 PfcCONH 2 -κP)] (5g), were determined by single-crystal X-ray diffraction analysis. All Pd(II) complexes were evaluated as catalysts in the cross-coupling of boronic acids and acyl halides to give ketones in a toluene/water biphasic mixture. Extensive reaction studies with compound 5e, which not only exerts good catalytic activity but is also readily accessible in a defined crystalline form, demonstrated efficient coupling reactivity for unsaturated substrates such as (substituted) benzeneboronic acids and benzoyl chlorides. The results also revealed that reaction difficulties encountered with less reactive substrates (e.g., insoluble aromatic boronic acids and all saturated aliphatic boronic acids) can be avoided by properly selecting the reaction partners, for example through transposition of substituents between reaction partners. Three representative benzophenones (4-fluoro-, 4-nitro-, and 4,4′-dinitrobenzophenone) were structurally characterized by single-crystal X-ray crystallography.

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Section: Resultssupporting

confidence: 80%

Synthesis, Structural Characterization, and Catalytic Evaluation of Phosphinoferrocene Ligands Bearing Extended Urea-Amide Substituents

Solařová¹,

Cı́sařová²,

Štěpnička³

2014

Organometallics

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“…A similar distortion, though to a lesser extent, was also noted for (PPh 3 ) 2 Ni(CO) 2 . 38 In the related palladium complexes, the OC-Pd-CO angle of 110.7°is much closer to an ideal tetrahedral angle. 39 While from literature precedent with bulky chelating phosphines 31am it might be expected that [( i Pr 3 P) 2 Ni] 2 N 2 (5) would react with CS 2 similarly to CO 2 to provide mononuclear ( i Pr 3 P) 2 Ni(η 2 -CS 2 ), the NMR data give no hint of such a product.…”

Section: Dalton Transactions Papermentioning

confidence: 93%

Synthesis and chemistry of bis(triisopropylphosphine) nickel(i) and nickel(0) precursors

et al. 2013

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High yield syntheses of ((i)Pr(3)P)(2)NiX (3a-c), (where X = Cl, Br, I) were established by comproportionation of ((i)Pr(3)P)(2)NiX(2) (1a-c) with ((i)Pr(3)P)(2)Ni(η(2)-C(2)H(4)) (2). Reaction of 1a with either NaH or LiHBEt(3) provided ((i)Pr(3)P)(2)NiHCl (4), along with 3a as a side-product. Reduction of ((i)Pr(3)P)(2)NiCl (3a-c) with Mg in presence of nitrogen saturated THF solutions provided the dinitrogen complex [((i)Pr(3)P)(2)Ni](2)(μ-η(1):η(1)-N(2)) (5). In aromatic solvents such as benzene and toluene a thermal equilibrium exists between 5 and the previously reported monophosphine solvent adducts ((i)Pr(3)P)Ni(η(6)-arene) (6a,b). Reaction of 5 with carbon dioxide provided ((i)Pr(3)P)(2)Ni(η(2)-CO(2)) (7). Thermolysis of 9 at 60 °C provided a mixture of products that included the reduction product ((i)Pr(3)P)(2)Ni(CO)(2) (8) along with (i)Pr(3)P=O, as identified by NMR spectroscopy. Complex 8 was also prepared in high yield from the reaction of 5 with CO. Reaction of 5 with CS(2) gave the dimeric carbon disulfide complex [((i)Pr(3)P)Ni(μ-η(1):η(2)-CS(2))](2) (9). Diphenylphosphine reacts with 5 to form the dinuclear Ni(I) complex [((i)Pr(3)P)Ni(μ(2)-PPh(2))](2) (10). Complex 5 reacts with PhSH to form ((i)Pr(3)P)(2)Ni(SPh)(H) (11), which slowly loses H(2) and (i)Pr(3)P to form the dimeric Ni(I) complex [((i)Pr(3)P)Ni(μ(2)-SPh)](2) (12) at room temperature. Complex 12 was also accessed by salt metathesis from the reaction of ((i)Pr(3)P)(2)NiCl (3a) with PhSLi, which demonstrates the utility of 3a as a Ni(I) precursor. With the exception of 6a,b, all compounds were structurally characterized by single-crystal X-ray crystallography.

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Density Functional Theory Calculations on Ni—Ligand Bond Dissociation Enthalpies

Wang¹,

Fu²,

Yu³

et al. 2014

Chinese Journal of Chemical Physics

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The formation and breaking of Ni—L (L=N-heterocyclic carbene, tertiary phosphine etc.) bond is involved in many Ni-catalyzed/mediated reactions. The accurate prediction of Ni—L bond dissociation enthalpies (BDEs) is potentially important to understand these Ni-complex involving reactions. We assess the accuracy of different DFT functionals (such as B3LYP, M06, MPWB1K, etc.) and different basis sets, including both effective core potentials for Ni and the all electron basis sets for all other atoms in predicting the Ni-L BDE values reported recently by Nolan et al. [J. Am. Chem. Soc. 125, 10490 (2003) and Organometallics 27, 3181 (2008)]. It is found that the MPWB1K/LanL2DZ:6-31+G(d,p)//MPWB1K/LanL2DZ:6-31G(d) method gives the best correlations with the experimental results. Meanwhile, the solvent effect calculations (with CPCM, PCM, and SMD models) indicate that both CPCM and PCM perform well.

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Dicarbonylbis(triphenylphosphine)nickel(0): a redetermination at 90 K

Abstract: Key indicatorsSingle-crystal X-ray study T = 90 K Mean '(C±C) = 0.001 A Ê R factor = 0.024 wR factor = 0.075 Data-to-parameter ratio = 83.4For details of how these key indicators were automatically derived from the article, see

Cited by 3 publications

References 6 publications

Synthesis, Structural Characterization, and Catalytic Evaluation of Phosphinoferrocene Ligands Bearing Extended Urea-Amide Substituents

Synthesis, Structural Characterization, and Catalytic Evaluation of Phosphinoferrocene Ligands Bearing Extended Urea-Amide Substituents

Synthesis and chemistry of bis(triisopropylphosphine) nickel(i) and nickel(0) precursors

Density Functional Theory Calculations on Ni—Ligand Bond Dissociation Enthalpies

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