Facile self-assembly of the first diphosphametacyclophane

Abstract

The reaction of isophthaloyl chloride and methyl-bis(trimethylsilyl)phosphane under mild conditions affords high yields of m-{-C(O)-C(6)H(4)(C(O)PMe)}(2) (1,10-dimethyl-1,10-diphospha-[3.3]-metacyclophane-2,9,11,18-tetraone): the first example of a diphosphametacyclophane.

Aroylphosphanes: Base‐Free Synthesis and Their Coordination Chemistry with Platinum‐Group Metals

“…Indeed, key geometric parameters for 1 are comparable to those of O=P{C(O)C 6 H 4 Me‐2} 3 ( 8 ,, Figure , Table ) in which the lone pair is sequestered. Moreover, upon formation of [Pt( 1 ) 2 Cl 2 ] the acyl linkages adjacent to the coordination site [ d C=O = 1.201(4), 1.208(4) Å] remain comparable to those distal [ d C=O = 1.215(4), 1.214(4) Å] and those within the free ligand [ d C=O = 1.211(3), 1.202(3), 1.220(3), 1.210(3) Å], while the P–C(O) linkages are similarly unperturbed [1.890(4)–1.897(3) Å, cf. 1.886(3)–1.894(3) Å for 1 ].…”

“…δ P , δ C , 1 J PC ) being wholly consistent with fully saturated phosphorus and classical ketone moieties, with no evidence for multiple‐bonding in the P–C linkage. Indeed, this situation is reflected in the structurally characterised cyclophane 1 , which exhibits carbonyl stretches of 1657 and 1639 cm –1 , but no geometric deviations to imply delocalisation, either in the solid state, or as computed for the gas phase…”

“…Herein, we describe the facile synthesis of a series of aroylphosphane derivatives and their coordination chemistry with representative platinum group metals. The synthesis and coordination chemistry of 1 has previously been reported in preliminary form …”

The impact of replacement of nitrogen with phosphorus atom in the pyromellitic diimides on their photophysical and electrochemical properties

“…As our research program for figuration of phosphorus-containing π-conjugated functional molecules, we focused on aromatic-fused diketophosphanyl compounds [13][14][15][16][17][18], which are regarded as phosphorus-analogues of rylene and related diimides [19,20]. Although a number of leading literature about the synthesis, structure, and reactivity of diketophosphanyl compounds exist, their physicochemical properties such as photophysical profiles and electrochemical behaviours have been scarcely explored [21][22][23][24][25][26].…”

η1:η2-P-Pyrazolylphosphaalkene Complexes of Ruthenium(0)

“…First described in 1985 [24], such systems remain relatively rare, though-with the exception of type E-all possible motifs have been realized, with P-metalla-(type A) and C-metalla-(type B) systems the most heavily studied. Recently, as part of an extended program investigating transition metal compounds featuring low-coordinate phosphacarbons with potential for conjugation [25][26][27][28], we have prepared and studied a range of ruthenaphosphaalkenyl complexes of the type [Ru{P=CH(SiMe2R)}Cl(CO)(PPh3)2] (R = Me 1a, Ph 1b, Tol 1c) [29,30]. These are prepared by hydroruthenation of phosphaalkynes R3SiC≡P, following from methodology developed initially by Hill and Jones for t BuC≡P and related systems [31][32][33], and superficially related to Nixon's independent reduction of [(Ph3P)2Pt(η 2 -P≡C t Bu)] with Schwartz's reagent [34].…”