Mercury(II) complexes of stabilized phosphine-phosphonium ylide derived from bis(diphenylphosphino)methane: Synthesis, spectra and crystal structures

The reaction of a mixed phosphine-phosphonium ylide, PPh₂CH₂PPh₂C(H)C(O)Ph with mercury(II) halides in methanol under mild conditions yielded the P, C-chelated complexes, [HgX₂(PPh₂CH₂PPh₂C(H)C(O)Ph)] where X = Cl (2), Br (3), I (4). Single crystal X-ray diffraction studies reveal the presence of mononuclear complexes containing Hg atom in a distorted tetrahedral environment and long Hg-C_ylide bond. The five-membered chelate rings in the two independent molecules present in the asymmetric unit of 4 adopt ‘envelope’ and ‘twist’ conformations. Spectroscopic studies also indicate the weaker Hg-C bonding. Additionally, the molecular structure of the free ylide (1) is also discussed.     

Transient terminal Cu-nitrene intermediates from discrete dicopper nitrenes

Reaction of the copper(I) beta-diketiminate {[Me3NN]Cu}2(mu-toluene) with the aryl azide N3Ar (Ar = 3,5-Me2C6H3) in toluene results in immediate effervescence and formation of the dicopper nitrene {[Me3NN]Cu}2(mu-NAr) (2) in 77% yield. The X-ray structure of 2 shows nearly symmetric bonding of the nitrene to two Cu centers separated by 2.911(1) A with Cu-N distances of 1.794(5) and 1.808(5) A along with a Cu-N-Cu angle of 107.8(2) degrees . This structure is conceptually related to the dicopper carbenes {[MexNN]Cu}2(mu-CPh2) (x = 2 or 3) (Dai, X.; Warren J. Am. Chem. Soc. 2004, 126, 10085. Badiei, Y. M.; Warren J. Organomet. Chem. 2005, 690, 5989.) which exhibit shorter Cu-Cu distances (2.4635(7) or 2.485(1) A) and acute Cu-C-Cu angles (79.51(14) or 80.1(2) degrees ). Addition of the Cu(I) anilidoimine {[Me2AI]Cu}2 (prepared from CuOtBu and the aniline-imine H[Me2AI] in 77% yield) to a benzene-d6 solution of 2 results in the formation of two new anilidoimine complexes {[Me2AI]Cu(mu- NAr)Cu[Me3NN] (5) and {[Me2AI]Cu}2(mu-NAr) (6) as well as [Me3NN]Cu(benzene) over 3 h. These observations are consistent with the slow dissociation of a [Me3NN]Cu fragment from 2 to generate the transient terminal nitrenes [Me3NN]Cu=NAr and [Me2AI]Cu=NAr quickly trapped by the [Me2AI]Cu fragment to form the new unsymmetrical and symmetrical dicopper nitrenes 5 and 6. Preliminary reactivity studies indicate electrophilic reactivity at the nitrene moiety. Dicopper nitrene 2 reacts with 10 equiv PMe3 and CNtBu to give ArN=PMe3 and ArN=C=NtBu in 94% and 92% yields, respectively, with concomitant formation of [Me3NN]Cu(L) (L = PMe3 and CNtBu). Reaction between 2 and 2 equiv PMe3 allows for observation of the structurally characterized Cu(I) phosphaimide [Me3NN]Cu(ArN=PMe3) (7).     

Thermal epimerization of inositol 1,3-benzylidene acetals in the molten state

1,3-O-Benzylidene-2,4,5,6-tetra-O-substituted-myo-inositol derivatives obtained by the DIBAL-H reduction of the corresponding myo-inositol 1,3,5-orthobenzoate derivatives undergo epimerization at the acetal carbon on heating, in the molten state, just above their melting point. The same epimerization reaction does not proceed either in the crystalline state or in solution. DFT calculations suggest that the epimeric acetal obtained by this thermal process is relatively more stable than the starting acetal. Either of these acetals could not be obtained by the reaction of the corresponding inositol derived diol with benzaldehyde. These observations constitute a novel reaction solely in the molten state, which are rarely encountered in the literature. X-ray crystal structures of the epimeric acetals as well as their radical deoxygenation reaction are also reported.