Rhenium(I) complexes of azadipyrromethene ligands are reported; three have been characterized crystallographically. The free ligands and their metallo-complexes undergo reductive electrochemistry. Red-light absorption results from optically allowed transitions to a ligand-localized LUMO.

The syntheses of benzoxaphospholes and new benzobisoxaphospholes that display blue fluorescence are presented. The latter compounds were accessed by the use of a new precursor, 2,5-diphosphinohydroquinone. The new compounds were fully characterized, including a structural study of 2,6-tert-butylbenzo[1,2-d;4,5-d']bisoxaphosphole. Quantum yields for photoluminescence were determined for a series of compounds. These materials feature bona fide P horizontal lineC p-p pi bonds suitable for conjugated materials having phosphorus as a participatory atom and can thus "photocopy" the properties of other conjugated organic molecules.

The diphosphene Mes*P=Mes* (Mes* = 2,4,6-tri-tert-butylphenyl; 1) reacted with 1 or 2 equiv of Au(tht)Cl (tht = tetrahydrothiophene) to produce the stable monoaurated adduct Mes*{AuCl}P=PMes* (2) or diaurated adduct Mes*{AuCl}P=P{AuCl}Mes* (3) respectively. The products were characterized by X-ray crystallography, UV-visible, IR, Raman, and multinuclear NMR spectroscopies, as well as by density functional theory calculations. The crystallographic and Raman spectroscopic data provide physical evidence that the P=P bond grows shorter and increases in strength upon auration; these observations are further examined by DFT calculations for a series of model compounds CH(3){AuCl}(n)P=P{AuCl}(n')CH(3) 1'-3' (n, n' = 0 or 1). Compounds 1-3 represent a rare series of crystallographically characterized diphosphenes bearing zero, one, or two AuCl units on each phosphorus atom, allowing for a systematic analysis of the impact of Lewis acids on the phosphorus-phosphorus double bond.

Treatment of d(1) [(nacnac)TiCl(Ntol(2))] with NaN(3) results in NaCl formation and N(2) ejection to yield the first four coordinate, parent imide [(nacnac)Ti=NH(Ntol(2))] (nacnac(-)=[ArNC(CH(3))](2)CH, Ar = 2,6-iPr(2)C(6)H(3), tol = 4-CH(3)C(6)H(4)).

Unlike the mythical Pushmi–Pullyu beast, push–pull stabilization of phosphinidenes is a reality. [ArP(AuCl)2PMe3] (Ar=aryl) represent interesting examples of phosphinidenes having both main group Lewis acid (LA) and Lewis base (LB) adducts. These materials have been structurally authenticated and show longer PP bonds and greater stabilization than of purely base‐stabilized phosphinidenes (in ArPPMe3).

b S Supporting Information ' RESULTS AND DISCUSSION Synthesis. Compounds 1-9 (Table 1) and 11-14 (Table 2) were reported previously and prepared according to published procedures. 17,18 The new benzoxaphosphole 10 was synthesized by analogous methods, i.e., via a cyclocondensation reaction between mesitylimidoyl chloride and 4-isopropyl-2-phosphinophenol in THF after refluxing for two days (Scheme 1). After removal of THF under vacuum, the remaining solid was extracted into hexane

No abstract

Anders als Doktor Dolittles Stoßmich‐Ziehdich ist die Push‐pull‐Stabilisierung von Phosphinidenen real: [ArP(AuCl)2PMe3]‐Spezies (Ar=Aryl) sind Phosphinidene (RP), die gleichzeitig mit Lewis‐Säuren (LA) und mit Lewis‐Basen (LB) zu Addukten zusammenlagern (siehe Bild). Die Addukte haben längere P‐P‐Bindungen und sind stabiler als rein basenstabilisierte Phosphinidene.