The molecular structure of a 2-aryl-1,3,2-dioxaphospholane and its coordination behaviour towards platinum(II) species; molecular structures of four platinum(II) complexes

Dillon, Keith B.; Goeta, Andrés E.; Monks, Philippa K.; Shepherd, Helena J.

doi:10.1016/j.poly.2009.07.040

Cited by 9 publications

(9 citation statements)

References 47 publications

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“…No 4 JP-F coupling was resolved, unlike 1 which yielded a 31 P septet at 158.2 ppm, 4 JP-F 35 Hz. [13] This observation parallels the behaviour in organo-chlorophosphanes andchlorophosphoranes bearing aromatic groups with CF3 substituents, where 4 JPF could be readily measured in the P(III) compounds, but not in their P(V) counterparts, formed by chlorination. [22] The shift to lower frequency from 1 to 2 is as expected for oxidation from P(III) to P(V), (a lower frequency shift of 64.…”

Section: (A) Reaction Of 1 With Elemental Seleniumsupporting

confidence: 73%

“…These complexes complement the platinum(II) derivatives reported previously for this ligand. [13] There are no direct analogues of the palladium compounds, although the gold(I) complex 5 parallels those reported by Schmutzler et al for two more sterically hindered 1,3,2-dioxaphospholanes. [10,11] Their ligands did not coordinate, however, to platinum(II), rhodium(I) or tungsten(0) metal fragments, indicating that 1 is a better ligand.…”

Section: Discussionmentioning

confidence: 53%

“…Elemental selenium and some metal complex starting materials were kindly provided by Dr. P. W. Dyer. The dioxaphosphole 1 was prepared as described previously; [12,13] its 31 P NMR solution-state spectrum was recorded to check for any phosphoruscontaining impurities before the complexation reactions were carried out. 31…”

Section: Methodsmentioning

confidence: 99%

“…The same general trends on complexation of 1 are observed in the present work as in the platinum(II) complexes synthesised previously. [13] There are slight reductions in the P -O and P -C bond lengths relative to those in the free ligand, and the OPO angle is widened (Table 4). These observations are mirrored by those for the AuCl complexes 7 and 9 of dioxaphospholanes 6 and 8 in the literature.…”

Section: (A) Reaction Of 1 With Elemental Seleniummentioning

confidence: 99%

“…[12] In a recent paper we reported the crystal and molecular structures of this compound, together with the synthesis of some platinum(II) complexes containing this ligand. [13] These coordination compounds were also characterised crystallographically. Because of the electron-withdrawing CF3 groups, 1 is expected to be a comparatively electron-poor donor.…”

Section: Introductionmentioning

confidence: 99%

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Coordination properties of a 2-aryl-1,3,2-dioxaphospholane

Coffer

Dillon

Howard

et al. 2018

Inorganica Chimica Acta

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Section: (A) Reaction Of 1 With Elemental Seleniumsupporting

confidence: 73%

Section: Discussionmentioning

confidence: 53%

Section: Methodsmentioning

confidence: 99%

Section: (A) Reaction Of 1 With Elemental Seleniummentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Coordination properties of a 2-aryl-1,3,2-dioxaphospholane

Coffer

Dillon

Howard

et al. 2018

Inorganica Chimica Acta

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Reactions of 1,3,2‐Diselenaphospholanes with Lewis Acids: Borane and (Pentamethylcyclopentadienyl)rhodium and ‐iridium Dichloride

2014

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2‐R‐1,3,2‐Diselenaphospholanes (R = iPr, Ph) with an annelated 1,2‐dicarba‐closo‐dodecaborane(12) unit were treated with Lewis acids such as borane reagents (BH3 in THF, and BH3–SMe2) as well as Cp*‐rhodium and ‐iridium dichloride (Cp* = pentamethylcyclopentadienyl). In all cases, the adduct formation in the beginning was followed by ring expansion through insertion of the borane or Cp*MCl2 into one of the P–Se bonds accompanied by transfer of a hydrido or chlorido ligand to phosphorus. Finally, the P–R unit was displaced from the ring to give the exchange products, in which the boron or the metal had become part of the five‐membered rings. The reactions were monitored by NMR spectroscopy (1H, 11B, 13C, 31P, and 77Se). The proposed reaction sequences were found to be in agreement with calculated [B3LYP/6‐311+G(d,p), LANL2DZ (Rh, Ir) level of theory] relative energies of optimized gas‐phase structures of the various products. The novel molecular structure of the preferred insertion product with M = Ir, R = iPr was determined by X‐ray analysis.

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New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation

Méjri

Fliss

Essalah

et al. 2022

Int J of Quantum Chemistry

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Oxidative addition of aliphatic amine on monocyclic 2-R-1,3,2-dioxaphospholane (R = methyl or phenyl) leading to phosphoranes bearing a P H axial bond was investigated using a combined theoretical and experimental approach. The reaction followed first order kinetics for both reactants. The activation parameters were consistent with a concerted mechanism exhibiting stereo, enantio, and regio specificities.Systematic density functional theory studies including reactivity descriptors, structural parameters, determination of all possible phosphorane isomers, their transition states and their formation mechanisms were carried out to delineate the reaction pathway. Depending on the nature of the atom in the final apical position (H, N of the amine, or C of the methyl), three types of phosphoranes were identified. Energy profiles, using the intrinsic reaction coordinate technique for the formation of each isomer, were established. It was shown that the phosphorus biphilicity acts in three consecutive sequences, namely nitrogen nucleophilic attack leading to a supermolecule structure, nucleophilic behavior of phosphorus in the transition state zone of influence, and electrophilic approach of the nitrogen atom to complete the reaction. Phosphorane with an equatorial P H bond was found to be a kinetic product that transforms rapidly to the thermodynamically stable isomer with axial P H via two consecutive Berry pseudo-rotations. A new tool, referred to reactive internal reaction coordinates, was introduced to represent the reaction path more clearly.

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The molecular structure of a 2-aryl-1,3,2-dioxaphospholane and its coordination behaviour towards platinum(II) species; molecular structures of four platinum(II) complexes

Cited by 9 publications

References 47 publications

Coordination properties of a 2-aryl-1,3,2-dioxaphospholane

Coordination properties of a 2-aryl-1,3,2-dioxaphospholane

Reactions of 1,3,2‐Diselenaphospholanes with Lewis Acids: Borane and (Pentamethylcyclopentadienyl)rhodium and ‐iridium Dichloride

New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation

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