meso-(1,1,4,7,10,10-Hexaphenyl-1,4,7,10-tetraphosphadecane-P,P',P'',P''')platinum(II) bis(tetraphenylborate)

Brüggeller, Peter; Nar, H.; Messerschmidt, Albrecht

doi:10.1107/s010827019100999x

Cited by 12 publications

(5 citation statements)

References 13 publications

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“…Due to the equilibrium between species and to the presence of an ionic structure the resonance at  18.7, assigned to P G , appears shifted to higher field compared to the resonances found for other neutral aminophosphine complexes containing linear PAuX moieties. 17 However, the reaction with AuI of the five-coordinate palladium(II) iodide 6, containing the tripodal tetraphosphine PP 3 , in 1 : 1 or 2 : 1 stoichiometric ratios occurs in the same way as the reaction between Au(tdg)X (X = Cl, Br) and [PdAu(PP 3 )X 2 ]X [X = Cl (4), Br (5)] there showing the resultant complexes [PdAu(PP 3 )I 2 ]I ( 16) and PdAu 2 (PP 3 )I 4 (22) the same structure as [PdAu(PP 3 )X 2 ]X [X = Cl ( 14), Br (15)] and PdAu 2 (PP 3 )X 4 [X = Cl (20), Br (21)], respectively.…”

Section: Effect Of the Halogen And The Polyphosphine On The Reactivit...mentioning

confidence: 84%

“…The reaction of the ligands NP 3 , PP 3 or P 4 in CH 2 Cl 2 or CHCl 3 with aqueous or methanolic solutions of the appropriate Pd(II) or Pt(II) precursor in 1 : 1 molar ratio leads to the synthesis of the mononuclear complexes [M(L)X]X (1-9) and [Pt(P 4 )](BPh 4 ) 2 (10). While the interaction between [Pd(NP 3 )X]X (1-3) (MeOH, CH 2 Cl 2 ) and Au(tdg)X (MeOH, Et 2 O) or commercial AuI only affords the heterobimetallic compounds PdAu(NP 3 )X 3 (11)(12)(13), complexes [M(PP 3 )X]X (4-9) (CHCl 3 ) react with gold(I) in 1 : 1 and 1 : 2 stoichiometric ratios achieving the mixed metal species [MAu(PP 3 )X 2 ]X (14)(15)(16)(17)(18)(19) and MAu 2 (PP 3 )X 4 [M = Pd (20)(21)(22), Pt (23)]. Another procedure to obtain complexes 20-23 consists of the addition of one equivalent of Au(I) to compounds 14-17.…”

Section: Synthesis Of Compoundsmentioning

confidence: 99%

“…This structure, proposed in solution (Scheme 2), coincides with the structure found in solid state. 22…”

Section: Complexes Containing Tris[2-(diphenylphosphino)ethyl]phosphinementioning

confidence: 99%

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Ring-opening reactions induced by gold(i) of five- and four-coordinate palladium(ii) and platinum(ii) complexes containing tripodal or linear polyphosphines

et al. 2004

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The tripodal ligands NP(3)(tris[2-(diphenylphosphino)ethyl]amine) and PP(3)(tris[2-(diphenylphosphino)ethyl]phosphine), form five-coordinate [Pd(NP(3))X]X [X = Cl (1), Br (2)], [M(PP(3))X]X [M = Pd: X = Cl (4), Br (5), I (6); M = Pt, X = Cl (7), Br (8), I (9)] and four-coordinate[Pd(NP(3))I]I (3) complexes containing three fused rings around the metal. The interaction between Au(tdg)X (tdg = thiodiglycol; X = Cl, Br) or AuI and the respective ionic halo complexes 1-9 in a 1:1 stoichiometric ratio occurs via a ring-opening reaction with formation of the heterobimetallic systems PdAu(NP(3))X(3)[X = Cl (11), Br (12), I (13)], [MAu(PP(3))X(2)]X [M = Pd: X = Cl (14), Br (15), I (16); M = Pt: X = Cl (17), Br (18), I (19)]. The cations of complexes 17 and 18 were shown, by X-ray diffraction, to contain a distorted square-planar Pt(II) arrangement (Pt(P(2)P)X) where PP(3) is acting as tridentate chelating ligand and an almost linear PAuX moiety bearing the dangling phosphorus formed in the ring-opening process. PPh(3) coordinates to Au(I) and not to M(II) when added in excess to 14 and 17. Complexes 14-17 and [Pt(P(4))](BPh(4))(2) (10) (P4=linear tetraphosphine) also react with A(I), via chelate ring-openings to give MAu(2)(PP(3))X(4) [M = Pd: X = Cl (20), Br (21), I (22); M = Pt: X = Cl (23)] and [Pt(2)Au(2)(mu-Cl)(2)(mu-P(4))(2)](BPh(4))(4) (24), respectively.

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Section: Effect Of the Halogen And The Polyphosphine On The Reactivit...mentioning

confidence: 84%

Section: Synthesis Of Compoundsmentioning

confidence: 99%

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Ring-opening reactions induced by gold(i) of five- and four-coordinate palladium(ii) and platinum(ii) complexes containing tripodal or linear polyphosphines

et al. 2004

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“…The ten-membered ring containing the two platinum atoms has a distorted twist-boat-chair-boat conformation of λ helicity, which is responsible for the M twist of the helicate. The crystal structures of (±)-[Pt{ R *, R *)-tetraphos}](BPh 4 ) 2 , [Pt{( R *, S *)-tetraphos}](BPh 4 ) 2 , and (±)-[PtH{( R *, R *)-tetraphos}]BPh 4 have been previously reported.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Electrochemistry of Di- and Zerovalent Nickel, Palladium, and Platinum Monomers and Dimers Derived from an Enantiopure (S,S)-Tetra(tertiary Phosphine)

et al. 2007

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The ligand (S,S)-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane, (S,S)-tetraphos, reacts with hexa(aqua)nickel(II) chloride in the presence of trimethylsilyl triflate (TMSOTf) in dichloromethane to give the yellow square-planar complex [Ni{(R,R)-tetraphos}](OTf)2, which has been crystallographically characterized as the square-pyramidal, acetonitrile adduct [Ni(NCMe){(R,R)-tetraphos}]OTf. Cyclic voltammograms of the nickel(II) complex in dichloromethane and acetonitrile at 20 degrees C showed two reduction processes at negative potentials with oxidative (E(p)(ox)) and reductive (E(p)(red)) peak separations similar to those observed for ferrocene/ferrocenium under identical conditions, suggesting two one-electron steps. The cyclic voltammetric data for the divalent nickel complex in acetonitrile at temperatures below -20 degrees C were interpreted according to reversible coordination of acetonitrile to the nickel(I) and nickel(0) complexes. The divalent palladium and platinum complexes [M{(R,R)-tetraphos}](PF6)2 and [M2{(R,R)-tetraphos}2](OTf)4 have been prepared. The reduction potentials for the complexes [M{(R,R)-tetraphos}](PF6)2 increase in the order nickel(II) < palladium(II) < platinum(II). The reaction of (S,S)-tetraphos with bis(cycloocta-1,5-diene)nickel(0) in benzene affords orange [Ni{(R,R)-tetraphos}], which slowly rearranges into the thermodynamically more stable, yellow, double-stranded helicate [Ni2{(R,R)-tetraphos}2]; the crystal structures of both complexes have been determined. The reactions of (S,S)-tetraphos with [M(PPh3)4] in toluene (M = Pd) or benzene (M = Pt) furnish the double-stranded helicates [M2{(R,R)-tetraphos}2]; the palladium complex crystallizes from hot benzene as the 2-benzene solvate and was structurally characterized by X-ray crystallography. In each of the three zerovalent complexes, the coordinated (R,R)-tetraphos stereospecifically generates tetrahedral M(PP)2 stereocenters of M configuration.

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“…Such complexes offer the interesting possibility of recognition of ligands on the basis of molecular size. The X-ray crystal structures of the square-planar complex [PtL]BPh4 (16) and some dimolybdenum complexes Mo2Br4L (17) have also been reported.…”

Section: Introductionmentioning

confidence: 99%

New dihydrogen complexes: the synthesis and spectroscopic properties of iron(II), ruthenium(II), and osmium(II) complexes containing the meso-tetraphos-1 ligand

Bautista¹,

Earl²,

Maltby³

et al. 1994

Can. J. Chem.

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Can. J. Chem. 72,547 (1994). The synthesis and properties of dihydrogen complexes trans-[MH(H2)L]+, M = Fe, Ru, Os, which contain the ligand mesotetraphos-1, S,R-Ph2PCH2CH2P(Ph)CH2CH2P(Ph)CH2CH2PPh2 (L) are described. There are interesting possibilities of isomerism in such trans complexes because the axial binding sites at the metal are different, one being surrounded by four phenyl groups and the other by two phenyl groups. The osmium complex is prepared in an unusual reaction of ci.~-p-Os(Cl)~L with HI, (1 atm) and NaBPh4 (1 mol) in THF or by the reaction of trans-OsH(C1)L with NaBPh4 and H2. The iron and ruthenium complexes were made by a reaction of HBF4 with complexes t r a n~-M ( H )~L that have inequivalent trans hydrides. The ruthenium complex was also prepared starting from isomers of t r a n s -R U H ( C~) L .~T~~ H-H distance in the rapidly spinning dihydrogen ligand has been calculated from Tl(min) data to be 0. [Traduit par la rtdaction]

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meso-(1,1,4,7,10,10-Hexaphenyl-1,4,7,10-tetraphosphadecane-P,P',P'',P''')platinum(II) bis(tetraphenylborate)

Cited by 12 publications

References 13 publications

Ring-opening reactions induced by gold(i) of five- and four-coordinate palladium(ii) and platinum(ii) complexes containing tripodal or linear polyphosphines

Ring-opening reactions induced by gold(i) of five- and four-coordinate palladium(ii) and platinum(ii) complexes containing tripodal or linear polyphosphines

Synthesis, Structure, and Electrochemistry of Di- and Zerovalent Nickel, Palladium, and Platinum Monomers and Dimers Derived from an Enantiopure (S,S)-Tetra(tertiary Phosphine)

New dihydrogen complexes: the synthesis and spectroscopic properties of iron(II), ruthenium(II), and osmium(II) complexes containing the meso-tetraphos-1 ligand

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