Evidence for horizontal transfer of 1-aminocyclopropane-1-carboxylate deaminase genes.

PCR was used to rapidly identify and isolate 1-aminocyclopropane-1-carboxylate (ACC) deaminase genes from bacteria. The Shimodaira-Hasegawa test was used to assess whether phylogenetically anomalous gene placements suggestive of horizontal gene transfer (HGT) were significantly favored over vertical transmission. The best maximum likelihood (ML) ACC deaminase tree was significantly more likely than four alternative ML trees, suggesting HGT.

Synthesis of enantiopure oxorhenium(V) and arylimidorhenium(V) "3 + 2" Schiff base complexes. X-ray diffraction, cyclic voltammetry, UV-vis, and circular dichroism characterizations.

Two new oxorhenium(V) and two new arylimidorhenium(V) complexes of the Schiff base ligands 2-hydroxybenzaldehyde-((1R,2S)-1-amino-2-indanol)imine (1) (H(2)L(1)) and 3-(1-adamantyl)-2-hydroxy-5-methylbenzaldehyde-((1R,2S)-1-amino- 2-indanol)imine (2) (H(2)L(2)) have been prepared from the reaction of the precursor Re(O)(PPh(3))(2)Cl(3), Re(NC(6)H(5))(PPh(3))(2)Cl(3), or Re(NC(6)H(4)OCH(3))(PPh(3))(2)Cl(3) and the free ligands H(2)L(1,2). The complexes Re(O)(HL(1))(L(1)) (3), Re(O)(HL(2))(L(2)) (4), Re(NC(6)H(5))(HL(1))(L(1)) (5), and Re(NC(6)H(4)OCH(3))(HL(1))(L(1)) (6) have been isolated and fully characterized by IR, (1)H NMR, circular dichroism, LRMS-FAB, and elemental analysis. All the complexes have a chiral center at rhenium. A single enantiomer is obtained in all cases. Suitable crystals of 3 and 5 were used in X-ray structural determinations. Crystal data: (3) C(32)H(27)N(2)O(5)Re.CH(2)Cl(2), orthorhombic, P2(1)2(1)2(1), a = 9.5599(16) A, b = 9.9579(16) A, c = 31.712(5) A, V = 3018.9(9) A(3), T = 100(2) K, Z = 4. (5) C(40)H(38)N(3)O(5)Re, monoclinic, P2(1), a = 9.286(3) A, b = 18.759(6) A, c = 9.957(3) A, beta = 102.817(6) degrees, V = 1691.3(10) A(3), T = 100(2) K, Z = 2. The major characteristic of these complexes is the presence of two coordination modes for the Schiff base ligands on rhenium, a tridentate ligand (noted L(1,2)) and another bidentate ligand (noted HL(1,2)). In the latter, the -OH group of the indanol is free and tilts away from the coordination sphere. X-ray structural analyses in conjunction with circular dichroism were used to assign the absolute configuration at rhenium (C). Cyclic voltammetry, UV-vis, and circular dichroism data are presented and discussed. The complexes were found to be highly stable and to resist reduction even when treated with organic phosphanes.

Kinetics and mechanisms of catalytic oxygen atom transfer with oxorhenium(V) oxazoline complexes.

The rhenium(V) monooxo complexes (hoz)2Re(O)Cl (1) and [(hoz)2Re(O)(OH2)][OTf] (2) have been synthesized and fully characterized (hoz = 2-(2'-hydroxyphenyl)-2-oxazoline). A single-crystal X-ray structure of 2 has been solved: space group = P1, a = 13.61(2) A, b = 14.76(2) A, c = 11.871(14) A, alpha = 93.69(4) degrees, beta = 99.43(4) degrees, gamma = 108.44(4) degrees, Z = 4; the structure was refined to final residuals R = 0.0455 and Rw = 0.1055. 1 and 2 catalyze oxygen atom transfer from aryl sulfoxides to alkyl sulfides and oxygen-scrambling between sulfoxides to yield sulfone and sulfide. Superior catalytic activity has been observed for 2 due to the availability of a coordination site on the rhenium. The active form of the catalyst is a dioxo rhenium(VII) intermediate, [Re(O)2(hoz)2]+ (3). In the presence of sulfide, 3 is rapidly reduced to [Re(O)(hoz)2]+ with sulfoxide as the sole organic product. The transition state is very sensitive to electronic influences. A Hammett correlation plot with para-substituted thioanisole derivatives gave a reaction constant rho of -4.6 +/- 0.4, in agreement with an electrophilic oxygen transfer from rhenium. The catalytic reaction features inhibition by sulfides at high concentrations. The equilibrium constants for sulfide binding to complex 2 (cause of inhibition), K2 (L x mol(-1)), were determined for a few sulfides: Me2S (22 +/- 3), Et2S (14 +/- 2), and tBu2S (8 +/- 2). Thermodynamic data, obtained from equilibrium measurements in solution, show that the S=O bond in alkyl sulfoxides is stronger than in aryl sulfoxides. The Re=O bond strength in 3 was estimated to be about 20 kcal x mol(-1). The high activity and oxygen electrophilicity of complex 3 are discussed and related to analogous molybdenum systems.