“…89 An investigation has been reported into a number of known and novel cyclopentadienyl-substituted phosphine ligands. 90 Also reported has been the use of simple cyclodiphosphazanes as probes in reactions such as the Mitsunobu and phosphine-catalysed reaction. 91 Reaction of pentelidene complexes [Cp*E{W(CO) 5 } 2 ] (E = P or As) with PH 2 Bu t results in the formation of species 33.…”
“…89 An investigation has been reported into a number of known and novel cyclopentadienyl-substituted phosphine ligands. 90 Also reported has been the use of simple cyclodiphosphazanes as probes in reactions such as the Mitsunobu and phosphine-catalysed reaction. 91 Reaction of pentelidene complexes [Cp*E{W(CO) 5 } 2 ] (E = P or As) with PH 2 Bu t results in the formation of species 33.…”
“…[1][2][3][4][5][6] In particular, when R 2 P fragments bind to Cp in an η 1 fashion, they can undergo two types of sigmatropic rearrangements (Scheme 1). [2,[7][8][9]] The R 2 P-Cp compound can either undergo a [1,5]-hydrogen shift, resulting in a vinylic isomer (B), or the R 2 P fragment of the allylic isomer (A) can migrate about the Cp ring via a so-called "circumambulatory rearrangement" (A to A'). In the case of uNHP Ar -Cp compounds (NHP = an N-heterocyclic phosphenium cation, where "u" denotes an unsaturated backbone and "Ar" is used to denote N-aryl substituents), only the allylic isomer A is observed.…”
Treatment of the N-heterocyclic chlorophosphine precursor (PPP)Cl (1) with two equivalents of nickelocene (NiCp 2 ) affords the phosphorus-bridged dimer [(µ-PPP)Ni 2 Cp 2 ]Cl (2). In contrast, an equimolar mixture of 1 and NiCp 2 in the presence of PPh 3 generates a different product, (PP(C 5 H 5 )P)NiCl 2 (3), in which a cyclopentadienyl anion has migrated to the N-heterocyclic phosphenium center. The phosphorus-bound Cp ring in complex 3 has undergone a [1,5]-hydride shift to afford a vinylic C 5 H 5 ring, and can be subsequently deprotonated to produce [(PP(C 5 H 4 )P)NiCl] (4).
A set of lithium phosphonium diylides Li[CH2-PR2-CpX] (9–12; CpX = C5Me4, C5H3
tBu, R = Ph, Me) is presented. Two of the
lithium
complexes were characterized by means of single-crystal X-ray analysis,
revealing a dimeric head-to-tail arrangement in the solid state. The
coordination behavior of 9–12 in
the liquid phase is solvent dependent. These lithium phosphonium diylides
exist as contact ion pairs in benzene and as solvent-separated ion
pairs in THF solutions. Phosphonium salts [H3C-PR2-CpXH)]+I– (1–4) are starting materials for the syntheses
of the title compounds and exist as mixtures of isomers due to [1,5]-prototropic
rearrangements. The dynamic behavior in solution has been investigated.
Two different routes allow access to title compounds 9–12. Reactions of 1–4 with 2 equiv of nBuLi give 9–12 in a one-pot synthesis. In an alternative
two-step route, dehydrodehalogenation of 1–4 with KH gives the corresponding phosphonium ylides 5–8. Two of these phosphonium ylides were
characterized by single-crystal X-ray analysis. In one case two different
conformers were obtained.
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