1,1,1-Tris(diphenylphosphinemethyl)ethane complexes of nickel and platinum with tin

Assis, Evilázio F. de; Filgueiras, Carlos A. L.

doi:10.1007/bf00136355

Cited by 8 publications

(4 citation statements)

References 11 publications

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“…The far infrared spectra (500-100 cm Ϫ1 ) for complexes 1 and 2 showed bands assignable, in agreement with the literature, 23 to the following bond vibrations: ν(Pd-Cl) = 318 cm Ϫ1 ; ν(Pt-Cl) = 320, 314 cm Ϫ1 ; ν(Pd-P) = 366, 353, 345 cm Ϫ1 ; ν(Pt-P) = 372, 356, 349 cm Ϫ1 . In the bimetallic complexes 3 and 4, ν(M-Cl) (290 cm Ϫ1 and 293 cm Ϫ1 , respectively) are at lower wave numbers compared to 1 and 2, consistent with relatively longer M-Cl distances for the above complexes.…”

Section: Infrared Spectrasupporting

confidence: 90%

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Gold(I)-induced chelate ring-opening of palladium(II) and platinum(II) triphos complexes

Sevillano¹,

Habtemariam²,

Parsons³

et al. 1999

J. Chem. Soc., Dalton Trans.

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The complexes [M(triphos)Cl]Cl [triphos = PhP(CH 2 CH 2 PPh 2 ) 2 ; M = Pd (1), M = Pt (2)] undergo ring-opening reactions with Au() to give [MAu(triphosIn these mixed metal complexes, triphos acts as a bidentate ligand for M and the third phosphorus atom is coordinated to Au() with a linear geometry. Complexes 1-4 were characterised by microanalysis, FAB mass spectrometry, IR, NMR ( 31 P and 195 Pt) spectroscopies and conductivity measurements. Complexes 2-4 were also characterised by X-ray crystallography. [Pt(triphos)Cl]Cl, 2, is monoclinic, space group P 2 1 /n, with square-planar geometry. The Pt-P central bond distance (2.207 Å) is shorter than the other two Pt-P distances (2.312 and 2.315 Å). [PdAu(triphos)Cl 3 ], 3, is also monoclinic (space group P 2 1 /n), with square-planar Pd() and linear Au() (P-Au-Cl 177.73Њ), and has a similar structure to complex 4, [PtAu(triphos)Cl 3 ] (monoclinic, space group I 2/a). The thiolate S of the tripeptide glutathione (GSH) and N-acetyl--cysteine binds to [Pt(triphos)] 2ϩ giving adducts with high aqueous solubility. In the presence of Au(), 5Ј-GMP displaced glutathione from [Pt(triphos)(GS)] ϩ to form two adducts. Both GSH and N-acetyl--cysteine readily extracted Au() from complex 4, [PtAu(triphos)Cl 3 ], to give complex 2, [Pt(triphos)Cl]Cl, and the Au() thiolate. Since chloride and thiolates would be strong competitors to DNA binding, proteins could be possible target sites for these complexes.

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Section: Infrared Spectrasupporting

confidence: 90%

“…Complex 1 was prepared using a variation of a literature method 23 which gave a higher yield than previously reported. 37 The route involved reaction of triphos and PdCl 2 in H 2 O-CH 2 Cl 2 (1 : 2) at ambient temperature and complex 1 was purified by recrystallization from CH 2 Cl 2 -n-hexane (1 : 2), giving a final yield of 68%.…”

Section: Preparationsmentioning

confidence: 99%

Gold(I)-induced chelate ring-opening of palladium(II) and platinum(II) triphos complexes

Sevillano¹,

Habtemariam²,

Parsons³

et al. 1999

J. Chem. Soc., Dalton Trans.

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“…Scheme 1 shows all complexes prepared with tris [2-(diphenylphosphino)ethyl]phosphine (PP 3 ). Complexes 1 ([Pd(PP 3 )Cl]Cl) and 2 ([Pt(PP 3 )Cl]Cl) were prepared as hydrates [(1)‚4H 2 O and (2)‚2H 2 O] starting from aqueous solutions of MCl 4 2salts and following a variation 19 of the method previously used by R. B. King et al 20 The reactions of 1 and 2 in CHCl Complexes 1-7 were prepared in excellent yields (81-92%), and the higher solubilities were found in coordinating solvents such as DMSO or DMF.…”

Section: Resultsmentioning

confidence: 99%

Preparation and Structural Characterization of Ionic Five-Coordinate Palladium(II) and Platinum(II) Complexes of the Ligand Tris[2-(diphenylphosphino)ethyl]phosphine. Insertion of SnCl₂ into M−Cl Bonds (M = Pd, Pt) and Hydroformylation Activity of the Pt−SnCl₃ Systems

et al. 2002

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The five-coordinate palladium(II) and platinum(II) complexes [M(PP(3))Cl]Cl [M = Pd (1), Pt (2)] (PP(3) = tris[2-(diphenylphosphino)ethyl]phosphine) were prepared by interaction of aqueous solutions of MCl(4)(2-) salts with PP(3) in CHCl(3). Complexes 1 and 2 undergo facile chloro substitution reactions with KCN in 1:1 and 1:2 ratios to afford complexes [M(PP(3))(CN)]Cl [M = Pt (3)] and [M(PP(3))(CN)](CN) [M = Pd (4), Pt (5)] possessing M-C bonds, both in solution and in the solid state. The reaction of 1 and 2 with SnCl(2) in CDCl(3) occurs with insertion of SnCl(2) into M-Cl bonds leading to the formation of [M(PP(3))(SnCl(3))](SnCl(3)) [M = Pd (6), M = Pt (7)]. The isolation as solids of complexes 6 and 7 by addition of SnCl(2) to the precursors requires the presence of PPh(3) which activates the cleavage of M-Cl bonds, favors the SnCl(2) insertion, and does not coordinate to M in any observable extent. Solutions of 6 in CDCl(3) undergo tin dichloride elimination in higher proportion than solutions of 7. The reaction of complexes 1 and 2 with SnPh(2)Cl(2) leads to [M(PP(3))Cl](2)[SnPh(2)Cl(4)] [M = Pd (8)]. Complexes 2, 5, 7, and 8 were shown by X-ray diffraction to contain distorted trigonal bipyramidal monocations [M(PP(3))X](+) [M = Pt, X = Cl(-) (2), X = CN(-) (5), X = SnCl(3)(-) (7); M = Pd, X = Cl(-) (8)], the central P atom of PP(3) being trans to X in axial position and the terminal P donors in the equatorial plane of the bipyramids. The "preformed" catalyst 7 showed a relatively high aldehyde selectivity compared to most of the platinum catalysts.

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“…We recently reported the synthesis of the square planar Nicomplex 2a and tetrahedral Ni-complex 2b from Triphos C (1a) and Triphos Si (1b) in the presence of NiCl 2 and described the reasons for their different structures. 18 In an attempt to establish a route for bimetallic nickel systems containing either a square planar or tetrahedral Ni-moiety, we set out to utilize the dangling phosphine as an additional metal binding site as was reported in mixed Ni II /Sn, 20 Ni 0 /Ni 0 , 21 as well as Ni 0 /Au I complexes 22 also comprising the Triphos C ligand.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Spontaneous Si–C bond cleavage in (Triphos^Si)-nickel complexes

et al. 2017

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Herein, we report on the versatile reactions of CHC(CHPPh) as well as CHSi(CHPPh) derived Ni-complexes. While Ni[CHC(CHPPh)] complexes reveal high stability, the Ni[CHSi(CHPPh)] analogs show rapid decomposition at room temperature and afford the unprecedented pseudo-tetrahedral phosphino methanide complex 5. We provide a detailed electronic structure of 5 from X-ray absorption and emission spectroscopy data analysis in combination with DFT calculations, as well as from comparison with structurally related complexes. A mechanistic study for the formation of complex 5 by reaction with BF is presented, based on a comparison of experimental data with quantum chemical calculations. We also show a simple route towards isolable Ni(i)-complexes on the gram scale.

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1,1,1-Tris(diphenylphosphinemethyl)ethane complexes of nickel and platinum with tin

Cited by 8 publications

References 11 publications

Gold(I)-induced chelate ring-opening of palladium(II) and platinum(II) triphos complexes

Gold(I)-induced chelate ring-opening of palladium(II) and platinum(II) triphos complexes

Preparation and Structural Characterization of Ionic Five-Coordinate Palladium(II) and Platinum(II) Complexes of the Ligand Tris[2-(diphenylphosphino)ethyl]phosphine. Insertion of SnCl₂ into M−Cl Bonds (M = Pd, Pt) and Hydroformylation Activity of the Pt−SnCl₃ Systems

Spontaneous Si–C bond cleavage in (Triphos^Si)-nickel complexes

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1,1,1-Tris(diphenylphosphinemethyl)ethane complexes of nickel and platinum with tin

Cited by 8 publications

References 11 publications

Gold(I)-induced chelate ring-opening of palladium(II) and platinum(II) triphos complexes

Gold(I)-induced chelate ring-opening of palladium(II) and platinum(II) triphos complexes

Preparation and Structural Characterization of Ionic Five-Coordinate Palladium(II) and Platinum(II) Complexes of the Ligand Tris[2-(diphenylphosphino)ethyl]phosphine. Insertion of SnCl2 into M−Cl Bonds (M = Pd, Pt) and Hydroformylation Activity of the Pt−SnCl3 Systems

Spontaneous Si–C bond cleavage in (TriphosSi)-nickel complexes

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Preparation and Structural Characterization of Ionic Five-Coordinate Palladium(II) and Platinum(II) Complexes of the Ligand Tris[2-(diphenylphosphino)ethyl]phosphine. Insertion of SnCl₂ into M−Cl Bonds (M = Pd, Pt) and Hydroformylation Activity of the Pt−SnCl₃ Systems

Spontaneous Si–C bond cleavage in (Triphos^Si)-nickel complexes