The study of organic matter in a well-preserved meteorite provides insight into processes that affected its parent asteroids.

Abstract-The distribution and isotopic and enantiomeric compositions of amino acids found in three distinct fragments of the Tagish Lake C2-type carbonaceous chondrite were investigated via liquid chromatography with fluorescence detection and time-of-flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. Large l-enantiomeric excesses (l ee 43-59%) of the a-hydrogen aspartic and glutamic amino acids were measured in Tagish Lake, whereas alanine, another a-hydrogen protein amino acid, was found to be nearly racemic (d l) using both techniques. Carbon isotope measurements of d-and l-aspartic acid and d-and l-alanine in Tagish Lake fall well outside of the terrestrial range and indicate that the measured aspartic acid enantioenrichment is indigenous to the meteorite. Alternate explanations for the l-excesses of aspartic acid such as interference from other compounds present in the sample, analytical biases, or terrestrial amino acid contamination were investigated and rejected. These results can be explained by differences in the solid-solution phase behavior of aspartic acid, which can form conglomerate enantiopure solids during crystallization, and alanine, which can only form racemic crystals. Amplification of a small initial l-enantiomer excess during aqueous alteration on the meteorite parent body could have led to the large l-enrichments observed for aspartic acid and other conglomerate amino acids in Tagish Lake. The detection of nonterrestrial l-proteinogenic amino acid excesses in the Tagish Lake meteorite provides support for the hypothesis that significant enantiomeric enrichments for some amino acids could form by abiotic processes prior to the emergence of life.

The silylated aryloxo ligands bis(o-silyloxyphenyl)phenylphosphine (abbreviated PhP{OT}(2)) and tris(o-trimethylsilyloxyphenyl)phosphine (abbreviated P{OT}(3), where T = Me(3)Si) were prepared. Complexation reactions with O=ReCl(2)(OEt)(PPh(3))(2) and O=ReCl(3)(PPh(3))(2) proceed by displacement of one PPh(3) and the subsequent stepwise replacement of the OEt and/or Cl substituents. The new complex Re(O)Cl(2)[kappa(2)-(P,O)-(PhP{O}{OT})](PPh(3)), formed by elimination of Me(3)SiOEt, exists in diastereomeric cis and trans forms. Elimination of a second equivalent of Me(3)SiCl gives Re(O)Cl[kappa(3)-(P,O,O)-(PhP{O}(2))](PPh(3)). Similarly P{OT}(3) converts Re(O)Cl(2)(OEt)(PPh(3))(2) to ReOCl(2)[kappa(2)-(P,O)-(P{O}{OT}(2))](PPh(3)) (5) (structurally characterized as 5.0.875CH(2)Cl(2)): crystal data; triclinic P&onemacr;, a = 14.302(4) Å, b = 18.734(2) Å, c = 17.639(4) Å, alpha = 80.950(12) degrees, beta = 80.12(2) degrees, gamma = 81.76(2) degrees, Z = 4. Final R(1) and wR(2) values are 0.0852 and 0.1525, respectively on F(o)(2) > 2sigma(F(o)(2)) data (or 0.1948 and 0.2019 on all data). The phenoxy phosphine ligand in 5 is bound via P and one O to Re. The P atoms are mutually cis to each other and to the terminal oxygen on Re. Two ortho-trimethylsiloxy substituted phenyl rings dangle from the coordinated phosphorus atom. Complex 5 can be converted to Re(O)Cl[kappa(3)-(P,O,O)-(P{O}(2){OT})](PPh(3)) (6) by treatment with PPN(+) Cl(-) and 6 was also obtained by direct reaction of Re(O)Cl(3)(PPh(3))(2) with P{OT}(3) at higher temperatures. The complex 6 has been structurally characterized: crystal data triclinic, P&onemacr;, a = 10.1509(6) Å, b = 12.1123(8) Å, c = 16.2142(14) Å, alpha = 97.851(7) degrees, beta = 94.852(7) degrees, gamma = 96.889(6) degrees, Z = 2. Final R(1) and wR(2) values were 0.0303 and 0.0721 on F(o)(2) > 2sigma(F(o)(2)) data (or 0.0348 and 0.0742 on all data). The phenoxyphosphine ligand in 6 is bound facially to Re through P and two of the phenoxy oxygens. The Ph(3)P group and terminal oxygen atoms are cis to the oxygen atoms of the phenoxy ligands and the Cl lies trans to P. One trimethylsiloxyphenol group dangles. Careful hydrolysis of 6 gave Re(O)Cl[kappa(3)-(P,O,O)-(P{O}(2){OH})](PPh(3)) which was also formed during complexation reactions in moist solvent. Solution (31)P{(1)H} NMR demonstrated cis- or trans-(P,P) geometry for the complexes, which was confirmed in the two aforementioned cases by structure determinations.

Abstract-The C2 ungrouped Tagish Lake meteorite preserves a range of lithologies, reflecting variable degrees of parent-body aqueous alteration. Here, we report on soluble organic compounds, including aliphatic and aromatic hydrocarbons, monocarboxylic acids, and amino acids, found within specimens representative of the range of aqueous alteration. We find that differences in soluble organic compounds among the lithologies may be explained by oxidative, fluid-assisted alteration, primarily involving the derivation of soluble organic compounds from macromolecular material. In contrast, amino acids probably evolved from precursor molecules, albeit in parallel with other soluble organic compounds. Our results demonstrate the role of parent-body alteration in the modification of organic matter and generation of prebiotic compounds in the early solar system, and have implications for interpretation of the complement of soluble organic compounds in carbonaceous chondrites.

Compound‐specific carbon isotope analysis (δ13C) of meteoritic organic compounds can be used to elucidate the abiotic chemical reactions involved in their synthesis. The soluble organic content of the Murchison carbonaceous chondrite has been extensively investigated over the years, with a focus on the origins of amino acids and the potential role of Strecker‐cyanohydrin synthesis in the early solar system. Previous δ13C investigations have targeted α‐amino acid and α‐hydroxy acid Strecker products and reactant HCN; however, δ13C values for meteoritic aldehydes and ketones (Strecker precursors) have not yet been reported. As such, the distribution of aldehydes and ketones in the cosmos and their role in prebiotic reactions have not been fully investigated. Here, we have applied an optimized O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine (PFBHA) derivatization procedure to the extraction, identification, and δ13C analysis of carbonyl compounds in the Murchison meteorite. A suite of aldehydes and ketones, dominated by acetaldehyde, propionaldehyde, and acetone, were detected in the sample. δ13C values, ranging from −10.0‰ to +66.4‰, were more 13C‐depleted than would be expected for aldehydes and ketones derived from the interstellar medium, based on interstellar 12C/13C ratios. These relatively 13C‐depleted values suggest that chemical processes taking place in asteroid parent bodies (e.g., oxidation of the IOM) may provide a secondary source of aldehydes and ketones in the solar system. Comparisons between δ13C compositions of meteoritic aldehydes and ketones and other organic compound classes were used to evaluate potential structural relationships and associated reactions, including Strecker synthesis and alteration‐driven chemical pathways.