Stereochemical studies of metal carbonylphosphorus trifluoride complexes

Clark, Ronald J.; Busch, Marianna A.

doi:10.1021/ar50067a005

Cited by 29 publications

(6 citation statements)

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“…Caled for C20H40IrP2SOgF3: C, 35.75; , 6.01. Found: C, 36.13; , 5.91. NMR ((CD3)2CO, 22 °C): b 5.35 (s, 2, H4/H5), 5.30 (s, 1, H2), 2.32 (s, 6, cp CHg's), 2.05-1.85 (complex m, 12, PEtg CH2's), (4). Method A: Reaction of lb with Methyl Iodide.…”

Section: Methodsmentioning

confidence: 99%

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Metallacyclohexadiene and metallabenzene chemistry. 3. Synthesis, characterization, and reaction chemistry of a family of 1-iridacyclohexa-2,4-diene complexes

Bleeke¹,

Peng²,

Xie³

et al. 1990

Organometallics

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Section: Methodsmentioning

confidence: 99%

“…31 | | NMR ((CD3)2CO, 22 °C): -22.4 (d, JP.P = 14. 4 Hz, 2, mutually trans PEtg's), -41.4 (t, Jp-p = 14.4 Hz, PEtg trans to Cl).…”

Section: Methodsmentioning

confidence: 99%

Metallacyclohexadiene and metallabenzene chemistry. 3. Synthesis, characterization, and reaction chemistry of a family of 1-iridacyclohexa-2,4-diene complexes

Bleeke¹,

Peng²,

Xie³

et al. 1990

Organometallics

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“…Compounds A series of tungsten carbonyls substituted with trifluorophosphine were synthesized by photochemical techniques previously published [7]. They were separated by preparative gas chromatography techniques [8] and the purity was checked by GC prior to neutron irradiation.…”

Section: Methodsmentioning

confidence: 99%

“…The sub-stitution of PF3 for CO introduces a non-equivalency which allows for identification of new species formed in the n, gamma event by gas chromatography. PF3 was chosen because of its bonding similarities to CO [7]. Irradiations were done on a series of W(PF3) x (CO)ex complexes (where χ = 0 to 3) both in the absence and presence of excess ligand gas.…”

Section: Introductionmentioning

confidence: 99%

Chemical Behavior of Tungsten Trifluorophosphines Following Neutron Activation

Bottomley

Clark

1988

Radiochimica Acta

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The chemical reactions that follow neutron capture have been studied for a series of tungsten trifluorophosphine carbonyls. The molecular distribution of 1,7 W was determined by gas chromatographic separation using scintillation detection. The chemical behavior of these compounds was examined in the condensed phase and the gas phase, both with and without excess PF 3 or CO. The retention of the parent species was measured as well as the formation of any scrambled species W(PF 3 ) x (CO) 6x in all experiments. The results of irradiations done in condensed phase with no excess ligands were modeled by a Simplex iterative routine to calculate the distribution of recoil fragments.

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“…Fluorophosphines, R n PF 3– n , and the parent compound PF 3 have been extensively studied, in part due to their exceptional ability to form coordination complexes of transition metals in low oxidation states .…”

Section: Introductionmentioning

confidence: 99%

Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX₃PF₂(X = F, Cl): A Computational Study

Nixon

Nyulászi

Szieberth

2015

Heteroatom Chemistry

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Detailed computational studies have been carried out to explain the unexpected differing reactions that occur between dimethylamine and the difluorophosphines, CX3PF2 (X = F, Cl). The reaction affords the thermodynamically controlled product chloroform in the case of X = Cl, whereas when X = F the analogous reaction pathway leading to fluoroform is hindered by a substantial reaction barrier in the gas phase, where the reaction should take place due to the volatility of the reactant. While the gas‐phase reaction energy gap is somewhat reduced when X = Cl, due to the stability of the migrating CCl3− moiety, the still substantial barrier does not account for the chloroform formation. Polarizable continuum model (PCM) calculations indicate a reduction of the barrier, facilitating the liquid‐phase reaction. The alternative gas‐phase reaction path, resulting in the aminolysis of a P—F bond is reversible and is shifted toward the product by capturing HF as the dimethylamino salt of the [CF3PF4H]− anion.

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Stereochemical studies of metal carbonylphosphorus trifluoride complexes

Cited by 29 publications

References 28 publications

Metallacyclohexadiene and metallabenzene chemistry. 3. Synthesis, characterization, and reaction chemistry of a family of 1-iridacyclohexa-2,4-diene complexes

Metallacyclohexadiene and metallabenzene chemistry. 3. Synthesis, characterization, and reaction chemistry of a family of 1-iridacyclohexa-2,4-diene complexes

Chemical Behavior of Tungsten Trifluorophosphines Following Neutron Activation

Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX₃PF₂(X = F, Cl): A Computational Study

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Stereochemical studies of metal carbonylphosphorus trifluoride complexes

Cited by 29 publications

References 28 publications

Metallacyclohexadiene and metallabenzene chemistry. 3. Synthesis, characterization, and reaction chemistry of a family of 1-iridacyclohexa-2,4-diene complexes

Metallacyclohexadiene and metallabenzene chemistry. 3. Synthesis, characterization, and reaction chemistry of a family of 1-iridacyclohexa-2,4-diene complexes

Chemical Behavior of Tungsten Trifluorophosphines Following Neutron Activation

Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX3PF2(X = F, Cl): A Computational Study

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Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX₃PF₂(X = F, Cl): A Computational Study