A Hypervalent Phosphorane–Palladium Cation Complex Bearing Benzaldehyde

Toyota, Koichiro; Yamamoto, Yohsuke; Akiba, Kin‐ya

doi:10.1039/a901668f

“…The P-O bond lengths [1.806(1)-1.807(1) Å] are considerably longer than those found in the hydroxyphosphorane [1.7059(18)-1.7421(18) Å], [50] but similar to those of 1b 1.780(3), 1.851(3) Å]. [51] The long P-O bond lengths indicated localisation of substantially negative charges on the oxygen atoms and weakening of the polar P-O bonds. The crystal structures of 3a and 3b were found to be in the Oapical pseudorotamer.…”

Section: X-ray Crystallographic Analysismentioning

confidence: 76%

“…8102(17)-1.8406(17) Å] and a phosphoranide-palladium complex, [(2-C6H4C(CF3)2O)2P-Pd(PhCHO)(dppe)](SbF6), [av.1.780(3), 1.851(3) Å] [51]. The long P-O bond lengths indicated localisation of substantially negative charges on the oxygen atoms and weakening of the polar P-O bonds.…”

mentioning

confidence: 99%

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

O'Brien¹,

Kano²,

Havare³

et al. 2020

Preprint

0

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The isolation and reactivities of two pentacoordinated<br>phosphorus–tetracoordinated boron bonded compounds were explored. A strong Lewis acidic boron reagent and electronwithdrawing ligand system were required to form the pentacoordinated phosphorus state of the P–B bond. The first compound, a phosphoranyl-trihydroborate, gave a THF stabilised phosphoranyl-borane intermediate upon a single hydride abstraction in THF. This compound could undergo a unique rearrangement reaction, which involved a two-fold ring expansion, to give a fused bicyclic compound or it could act as a mono-hydroboration reagent. The hydroboration reactivity of the intermediate was found to be more reactive towards alkynes over alkenes with good to moderate regioselectivity towards the terminal carbon. The second compound, a phosphoranyl-triarylborate, was found to have different reactivity as it was highly stable towards acids and bases. This is thought to be due to the large bulk around the P–B bond as shown in the crystal structure.<br>

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“…The P–O bond lengths [1.806(1)‐1.807(1) Å] are considerably longer than those found in the hydroxyphosphorane [1.7059(18)‐1.7421(18) Å], but similar to those of 1b [1.8102(17)‐1.8406(17) Å] and a phosphoranide‐palladium complex, [(2‐C 6 H 4 C(CF 3 ) 2 O) 2 P–Pd(PhCHO)(dppe)](SbF 6 ), [av. 1.780(3), 1.851(3) Å] . The long P–O bond lengths indicated localisation of substantially negative charges on the oxygen atoms and weakening of the polar P–O bonds.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

O'Brien

¹

,

Kano

²

,

Havare

³

et al. 2020

View full text Add to dashboard Cite

The isolation and reactivities of two pentacoordinated phosphorus-tetracoordinated boron bonded compounds were explored. A highly Lewis acidic boron reagent and electron-withdrawing ligand system were required to form the pentacoordinated phosphorus state of the P-B bond. The first compound, a phosphoranyl-trihydroborate, gave a THF stabilised phosphoranyl-borane intermediate upon a single hydride abstraction in THF. This compound could undergo a unique rearrangement, which involved a two-fold ring expansion, to give [ ‡] Current address:

show abstract

“…The P-O bond lengths [1.806(1)-1.807(1) Å] are considerably longer than those found in the hydroxyphosphorane [1.7059( 18)-1.7421( 18) Å], [50] but similar to those of 1b . [51] The long P-O bond lengths indicated localisation of substantially negative charges on the oxygen atoms and weakening of the polar P-O bonds. The crystal structures of 3a and 3b were found to be in the Oapical pseudorotamer.…”

Section: X-ray Crystallographic Analysismentioning

confidence: 99%

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

O'Brien¹,

Kano²,

Havare³

et al. 2020

Preprint

0

View full text Add to dashboard Cite

The isolation and reactivities of two pentacoordinated<br>phosphorus–tetracoordinated boron bonded compounds were explored. A strong Lewis acidic boron reagent and electronwithdrawing ligand system were required to form the pentacoordinated phosphorus state of the P–B bond. The first compound, a phosphoranyl-trihydroborate, gave a THF stabilised phosphoranyl-borane intermediate upon a single hydride abstraction in THF. This compound could undergo a unique rearrangement reaction, which involved a two-fold ring expansion, to give a fused bicyclic compound or it could act as a mono-hydroboration reagent. The hydroboration reactivity of the intermediate was found to be more reactive towards alkynes over alkenes with good to moderate regioselectivity towards the terminal carbon. The second compound, a phosphoranyl-triarylborate, was found to have different reactivity as it was highly stable towards acids and bases. This is thought to be due to the large bulk around the P–B bond as shown in the crystal structure.<br>

show abstract

A Hypervalent Phosphorane–Palladium Cation Complex Bearing Benzaldehyde

Abstract: is prepared by the reaction of Rf 2 PPdClPh 2 PCH 2 CH 2 PPh 2 1 with AgSbF 6 in the presence of benzaldehyde in 92% yield, and the structure determined by X-ray diffraction analysis.

Cited by 15 publications

References 15 publications

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds

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