Preparation and proton magnetic resonance spectra of some tetrakis(arylmethylphosphine)platinum(0) and - palladium(0) compounds

Clark, H. C.; Itoh, K.

doi:10.1021/ic50102a035

Cited by 22 publications

(7 citation statements)

References 3 publications

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“…These products (trans-PtPh 2 (PMe 2 Ph) 2 and Ph 4 Ge) were identified by comparison with their spectroscopic data reported previously [10]. The formation of Pt(PhMe 2 P) 4 was also confirmed by its 1 H and 31 P NMR spectra [11]. The yield of Pt(PhMe 2 P) 4 was roughly estimated (ca.…”

Section: Thermal Reactivity Of Trans-pt(ph 3 Ge) 2 (Pme 2 Ph)supporting

confidence: 58%

Thermal reactivity of cis- and trans-bis(triphenylgermyl)bis(tertiary phosphine)platinum(II)

Mochida

Fukushima

Suzuki

et al. 2007

Journal of Organometallic Chemistry

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Section: Thermal Reactivity Of Trans-pt(ph 3 Ge) 2 (Pme 2 Ph)supporting

confidence: 58%

Thermal reactivity of cis- and trans-bis(triphenylgermyl)bis(tertiary phosphine)platinum(II)

Mochida

Fukushima

Suzuki

et al. 2007

Journal of Organometallic Chemistry

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“…Phosphorus NMR signals arising from both the endo- and the exo-phosphorus centers in the Pd(0) complex ( 6 ) appeared much broader than those for the analogous Pd II complex 5 , but no free phosphole signal was observed in contrast to behavior of previously investigated Pd 0 L 4 complexes of aryl- and alkylphosphines . These broad signals were not sharpened by cooling the 31 P{ 1 H} NMR sample to −75 °C in either of the Pd 0 or the Pd II cases so it does not appear that there is a facile ligand exchange.…”

Section: Resultsmentioning

confidence: 77%

“…The reaction of Pt(cod)ClMe with 1 gave, ultimately, an unexpected reductive−elimination reaction product, Pt 0 ( 1 ) 4 ( 9 ), isolated from the reaction mixture as an orange crystalline solid. Complex 9 also showed slightly broad 31 P NMR spectra, but no evidence for free phosphole was observed in contrast to the typical behavior of Pt(0) complexes of organophosphines . The 31 P NMR spectrum of 9 was characterized by a large value of 1 J PPt (5050 Hz) and by an increased 2 J PP (159 Hz) coupling.…”

Section: Resultsmentioning

confidence: 88%

Chemistry of Heterobifunctional Diazaphospholylphosphines. 4. Complexation and Reduction Reactions of Platinum(II) and Palladium(II) with Phosphine-Substituted (Fluoro, Dimethylamino, Trifluoroethoxy) 4-Phosphino-2,5-dimethyl-2H-1,2,3σ²-diazaphospholes. Structure of a Novel Platinum(0) Tetrakis(difluorophosphine) Complex

1999

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Selected platinum(II) and palladium(II) complexes react with 4-(difluorophosphino)-2,5-dimethyl-2H-1,2,3σ2-diazaphosphole (LF) to form the expected X2M(LF)2 complexes. In some cases, redox processes yield stable, solid, M0(LF)4 complexes; thus Pd(cod)Cl2 with LF gave a mixture of the Pd0 and PdII complexes whereas Pt(cod)Cl2 gave only the Pt(LF)2Cl2 complex. With limited LF, (cod)Pt(Me)Cl gave the expected (LF)2Pt(Me)Cl complex, but when the reaction was carried out with excess LF, PtII was reduced to Pt0 to form the Pt0(LF)4 complex. This complex was structurally characterized. Crystal data for C16H28F8N8O2P8Pt: tetragonal, I4̄2m (No. 121), a = 11.961(2) Å, c = 15.034(3) Å, V = 2150.8(6) Å3, Z = 2. Final indices: GOF = 1.299 [F o 2 ≥ −3σ(F o 2)] and R 1 = 0.0381, wR 2 = 0.1180 (for F o 2 > 2σ(F o 2)) and R 1 = 0.0395, wR 2 = 0.1188 for all data. The structure around the Pt0 atom was revealed as a slightly squashed tetrahedron surrounded by four phospholylphosphine ligands coordinated through the exocyclic phosphine. The Pt−P distance is 2.237(3) Å. The Pd(LF)4 analogue was also isolated in pure form from the reaction of LF with Pd2(dba)3. The related 4-(bis(dimethylamino))-2,5-dimethyl-2H-1,2,3σ2-diazaphosphole (LN) displaced cod from M(cod)Cl2 (M = Pd, Pt) to give only the (LN)2MCl2 complexes (M = Pd and Pt) with no evidence for reduction of the metal center. The larger steric bulk of LN is presumably also the reason this ligand forms the trans complex instead of the cis complexes which were formed by LF from the same precursors in analogous reactions. The reaction of LN with (cod)Pt(Me)Cl produced only cis-(LN)2Pt(Me)Cl; there was no evidence of reduction to Pt0 in contrast to the behavior of LF. With LF, the stereochemistry of the final product was the same as that of the starting material. The third ligand, 4-(bis(trifluoroethoxy)phosphino)-2,5-dimethyl-2H-1,2,3σ2-diazaphosphole (LO) gave the expected platinum cis complex (LO)2MCl2 from the (cod)MCl2 precursor, but palladium rearranged during the complexation reaction to form the trans complex. Again, no evidence for reduction of either Pt or Pd was observed with LO.

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“…13 The complex Pt[P(CH3)(C6Hs)2]4 was prepared according to the method of Clark and Itoh. 5 All reactions were carried out under dry nitrogen but the subsequent manipulations of reaction mixtures were performed in air.…”

Section: Methodsmentioning

confidence: 99%

Preparation and variable-temperature nuclear magnetic resonance studies of tris(diphenyltrifluoromethylphosphine)platinum(0)

Attig¹,

Beg²,

Clark³

1975

Inorg. Chem.

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The preparation of tris(diphenyltrifluoromethylphosphine)platinum(O) is described. show that the rapid phosphine exchange occurring at room temperature is frozen out at ca. -50" and that at lower temperatures a further dynamic process, possibly associated with rotation of phosphine about the Pt-P bond, is reduced in rate, Similar studies of dichloromethane solutions of the title compound in the presence of different excesses of free phosphine show the formation of the tetrakis complex and of a new previously unobserved species. The possible nature of this new species is discussed. IntroductionA large number of zerovalent platinum compounds are now known, many of which contain a tertiary phosphine as the stabilizing ligand. Aryl-,l-3 alkyl-,4 arylalkyl-,5,6 alkylperfluoroaryl-,5,6 and fluorophosphines7 have been used for this purpose. Tri-and tetracoordinate species have long been known as stable solids, although in certain cases5.8 dissociation of the tetrakis complex occurs in solution to the tris complex and free phosphine. Moreover, rapid phosphine-exchange processes have been observed in solution for a number of the complexes. Dissociation of the tetrakis to the tris complexes has been observed only for the triaryl-and alkyldiarylphosphine

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Preparation and proton magnetic resonance spectra of some tetrakis(arylmethylphosphine)platinum(0) and - palladium(0) compounds

Cited by 22 publications

References 3 publications

Thermal reactivity of cis- and trans-bis(triphenylgermyl)bis(tertiary phosphine)platinum(II)

Thermal reactivity of cis- and trans-bis(triphenylgermyl)bis(tertiary phosphine)platinum(II)

Preparation and variable-temperature nuclear magnetic resonance studies of tris(diphenyltrifluoromethylphosphine)platinum(0)

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