The trans-influence of acyl groups in trans-[PtCl(COR)(PPh3)2] complexes

Dent, Stephen P.; Eaborn, Colin; Pidcock, Alan; Ratcliff, B.

doi:10.1016/s0022-328x(00)88312-6

Cited by 20 publications

(16 citation statements)

References 7 publications

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“…The carbonyl stretching frequencies in complexes 5 and 6 were found near 1650 cm -1 . These frequencies are characteristic for complexes trans -[PtCl(COR)(PPh 3 ) 2 ] . Contrary to the A-frame complex 6b , complex 6a shows two ν(CO) (1650, 1656 cm -1 ), indicating a slight asymmetry in the Pt−Cl−Pt bridge.…”

Section: Resultsmentioning

confidence: 90%

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Reactivity of Dinuclear Platina-β-diketones toward Phosphines and Pyridines: Formation of Mononuclear Platina-β-diketones and Acyl(chloro)platinum(II) Complexes

et al. 1999

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Dinuclear platina-β-diketones [Pt2{(COR)2H}2(μ-Cl)2] (R = Me (1a), Et (1b)) react with phosphines (PPh3, Ph2P(CH2) n PPh2, n = 1−3) and triphenylarsine to form acylplatinum(II) complexes as well as acetaldehyde and propionaldehyde, respectively. Reaction of 1 with 4 equiv of PPh3 and AsPh3 leads to trans-[PtCl(COR)L2] (L = PPh3 (4), AsPh3 (5); R = Me (a), Et (b)). Reaction of 1a with PPh3 in a 1:2 molar ratio results in formation of carbonyl(methyl)platinum complexes [PtCl(Me)(CO)(PPh3)] (11). Cationic A-frame complexes [Pt2(COR)2(μ-Cl)(μ-dppm)2]Cl (R = Me (6a), Et (6b)) were formed in reactions of 1 with 2 equiv of Ph2PCH2PPh2 (dppm). Treatment of 1a with Ph2P(CH2)2PPh2 (dppe) and Ph2P(CH2)3PPh2 (dppp) yields complexes [PtCl(COMe){Ph2P(CH2) n PPh2}] (n = 2 (7), 3 (8)). However, at low temperatures (−30 °C) reactions of 1a with dppe and dppp afford mononuclear cationic platina-β-diketones [Pt{(COMe)2H}(Ph2P(CH2) n PPh2)]Cl (n = 2 (9a), 3 (10)). The reaction of [Pt2{(COMe)2H}2(μ-Cl)2] (1a) with pyridine (py) or quinoline (quin) results in cleavage of the Pt−Cl−Pt bridges, yielding mononuclear neutral platina-β-diketones [PtCl{(COMe)2H}L] (L = py (13a), quin (13b)). In the solid state complex 13b reveals a nonplanar arrangement of the platina-β-diketone unit with a strong hydrogen bond (O···O 2.419(8) Å). From all these findings the mechanism of the aldehyde formation in the reactions of platina-β-diketones 1 with L (PPh3, AsPh3) and LL (dppm, dppe, dppp) is deduced.

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Section: Resultsmentioning

confidence: 90%

“…Complexes 7-10 were characterized by NMR ( 1 H, 13 C, 31 P) and IR spectroscopy. The 31 P NMR spectroscopic data of [PtCl(COMe)(dppp)] ( 8) agree with literature data.…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Dinuclear Platina-β-diketones toward Phosphines and Pyridines: Formation of Mononuclear Platina-β-diketones and Acyl(chloro)platinum(II) Complexes

et al. 1999

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“…22 Similarly, Pt(Ph3P)2Cl-(COPh) was shown to contain trans phosphines by 31P nmr. 13 The geometry of the carbomethoxy complex Pt(Ph3P)2Cl-(C02Me) was assumed to be trans by analogy with the corresponding Ph2PMe complex.23 Geometries have been assigned to the dihalide complexes on the basis of the number of observed metal-halogen stretching bands.24 These bands, listed in Table I, are readily identified by their sensitivity to halogen substitution and their intensity, particularly in the Raman. 25,26 Typical infrared spectra are shown in Figure 1, together with the spectrum of free Ph3P.…”

Section: Resultsmentioning

confidence: 99%

Assignment of stereochemistry in bis(triphenylphosphine)platinum(II) complexes

Mastin¹

1974

Inorg. Chem.

135

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“…In Figure 5, the peak at 1610 cm -1 in the HREEL spectrum after acetaldehyde adsorption on Pd(110) at 150 K is assigned to the ν(CO) mode of acetyl adspecies. By comparison with organometallic platinum and palladium acetyl complexes, 21,22 ν(CO) modes for acetyl species from acetaldehyde reactions on Pt(S)-[6(111) × (100)] 6 and Pd(111) 4 surfaces have been identified at 1650 and 1595 cm -1 , respectively. The losses due to the CO stretching mode of the acetyl ligand in the stable trans-[PdBr(COCH 3 )(PEt 3 ) 2 ] complexes 22 range from 1661 to 1675 cm -1 where the acetyl ligand is coordinated to the metal center via its unsaturated carbonyl carbon atom, i.e., in an η 1 -(C) configuration.…”

Section: Tpd and Hreels Of Acetaldehyde On Pd(110)mentioning

confidence: 99%

Adsorption and Reaction of Aldehydes on Pd Surfaces

Shekhar¹,

Barteau²,

Plank³

et al. 1997

J. Phys. Chem. B

130

116

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Aldehydes have been proposed as important intermediates during alcohol synthesis on supported transition metal catalysts. To develop insights into higher oxygenate syntheses, adsorption and reaction of aldehydes on transition metal surfaces and the surface structure dependence of these processes are considered here. In this work, the adsorption and reactions of acetaldehyde and propionaldehyde on Pd(110) surfaces were investigated with temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy techniques. The slate of desorption products observed in TPD experiments following acetaldehyde adsorption on the clean Pd(111) and Pd(110) surfaces was the same: CO, H2, CH4, and CH3CHO were observed in both cases. Likewise, propionaldehyde decomposition gave rise to CO, H2, C2H4, and C2H6 on both surfaces. However, acetaldehyde isotope-labeling experiments indicated that methyl groups were released following decarbonylation reactions of acetaldehyde on Pd(110), in contrast with earlier suggestions of methylene release on the clean Pd(111) surface. Further studies on H- and D-precovered Pd(110) surfaces elucidated the competing decomposition and hydrogenation pathways as well as the distribution of hydrocarbon species released after decarbonylation of adsorbed aldehydes on Pd(110). These results demonstrate that a variety of surface hydrocarbon ligands can be produced by aldehyde decarbonylation on palladium surfaces and imply that higher oxygenate synthesis by carbonylation of surface hydrocarbon fragments may involve an equally large variety of hydrocarbon intermediates on supported metal catalysts.

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The trans-influence of acyl groups in trans-[PtCl(COR)(PPh3)2] complexes

Cited by 20 publications

References 7 publications

Reactivity of Dinuclear Platina-β-diketones toward Phosphines and Pyridines: Formation of Mononuclear Platina-β-diketones and Acyl(chloro)platinum(II) Complexes

Reactivity of Dinuclear Platina-β-diketones toward Phosphines and Pyridines: Formation of Mononuclear Platina-β-diketones and Acyl(chloro)platinum(II) Complexes

Assignment of stereochemistry in bis(triphenylphosphine)platinum(II) complexes

Adsorption and Reaction of Aldehydes on Pd Surfaces

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