Bis(triphenylphosphoniumyIidyl)phosphane

Abstract

Ylides, Transylidation, Phosphenium Ions, M ichaelis Arbusov Rearrangement, DiphosphanesBis(ylidyl)phosphanes can be prepared from ylides and dichlorophosphanes or from bis-(ylidyl)phosphenium chlorides and organolithium compounds. By substituting in bis(ylidyl)-phosphenium chlorides the chloride ion for more basic anions, a large variety o f bis(ylidyl)-phosphanes is accessible. They can be protonated at the ylidic carbon atoms, but alkylated and oxidized at the central phosphorus atom. A s shown by 3IP NM R in solution and by Xray investigation of the crystal, the lone pair at the tervalent phosphorus is generally oriented synperiplanar to both phosphonio groups.

Reactions of Bis(triphenylphosphonio)isophosphindolide Salts with Mercury(II) Compounds: Coordination Induced Addition and Oxidation Reactions and Synthesis of a Monomeric 1:1 Complex of the Type [R2(R‘O)P]HgBr2

“…The different metal NMR data of 4 and 5 suggest that the binuclear unit of 5 is preserved in solution and the P-substituted metal is connected to one chloride and one [HgCl 4 ] 2- ligand, while in 4 it carries two chlorides. Complex 8 displays significantly higher values of 2 J PP than those of 4 and 5 , presumably due to the lower coordination number of the intermediate carbon . The magnitude of 1 J HgP is much larger than that in complexes [(R 3 P)HgX 2 ] 2 (X = halogen, 1 J HgP = 4200−7200 Hz 13 ); similar couplings were reported for (Mes 3 P)Hg(NO 3 ) 2 (10 278 Hz 14 ) and phosphite complexes such as [((EtO) 3 P) 2 HgCl 2 ] 2 (11 300 Hz 15 ).…”

“…Complex 8 displays significantly higher values of 2 J PP than those of 4 and 5, presumably due to the lower coordination number of the intermediate carbon. 12 The magnitude of 1 J HgP is much larger than that in complexes [(R 3 P)HgX 2 ] 2 (X ) halogen, 1 J HgP ) 4200-7200 Hz 13 ); similar couplings were reported for (Mes 3 P)-Hg(NO 3 ) 2 (10 278 Hz 14 ) and phosphite complexes such as [((EtO) 3 P) 2 HgCl 2 ] 2 (11 300 Hz 15 ). Following common explanation patterns, 10 the large couplings may be related with a low metal coordination number and high degree of s-character in the Hg-P bond.…”

Molecules that we made: An essay on phosphorus chemistry

“…Intramolecular versions of this substitution resulted in the diphosphaindene 64 [173] and the diphosphanaphthalene cation 65 [174].…”

Ylide‐Stabilized Phosphenium Cations: Impact of the Substitution Pattern on the Coordination Chemistry

“…[11] Nonetheless, these systems exhibit phosphenium cation reactivity and for example react with nucleophiles such as organolithium compounds at the central phosphorus atom. [12] However, the coordination chemistry of ylidephosphenium cations remains almost unexplored. To the best of our knowledge, only the coordination chemistry of bisphosphonio-isophosphindolides of type A has been explored.…”

“…In case of the cyclic cation A this delocalization even results in a partial phosphide character at the central P atom ( A 3 , Figure 1). [11] Nonetheless, these systems exhibit phosphenium cation reactivity and for example react with nucleophiles such as organolithium compounds at the central phosphorus atom [12] . However, the coordination chemistry of ylidephosphenium cations remains almost unexplored.…”