Results for “RHODIUM 93”

DOE OSTI2011

Nuclear Data Sheets for A = 93

Nuclear structure data pertaining to all nuclei with mass number A=93 (Se, Br, Kr, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag) have been compiled and evaluated and incorporated into the ENSDF data file. This publication for A=93 supersedes the previous publication by C.M. Baglin, Nuclear Data Sheets80, 1 (1997) (literature cutoff date November 1996) and subsequent revisions by C.M. Baglin of the ENSDF files for 93Br and {sup 93}Kr (literature cutoff 26 February 2001) and for {sup 93}Rh (literature cutoff 27 February 2001); it includes all data available prior to 15 December 2010. Significant changes since prior evaluations include the following: 2010Hw03 identified several high-spin states in {sup 93}Kr in {sup 252}Cf SF decay; in addition to the many low-spin levels already known in {sup 93}Rb from {beta}{sup -} decay, several higher-spin states have now been identified in a {sup 252}Cf SF decay study (2009Hw03); this SF decay has also been used to identify additional states in {sup 93}Sr (2003Hw01) and the {sup 238}U({sup 82}Se,X{gamma}) reaction (2007Bu35) has provided new information on {sup 93}Y. (HI,xn{gamma}) reaction studies have expanded our knowledge of the structure of {sup 93}Zr (2002Fo03, 2005Pa48), {sup 93}Nb (2007Wa45), {sup 93}Mo (2005Fu01), {sup 93}Tc (2003Ha22) and {sup 93}Pd (2004So04,2004Ru02). Considerable information on {sup 93}Nb was provided by a (p,2n{gamma}) study (2010Or01, 2006Or09, 2007Or01). The level schemes of {sup 93}Ru, {sup 93}Rh and {sup 93}Pd have undergone the most extensive revision thanks to studies of {sup 93}Rh {epsilon} decay (2004De40), {sup 94}Ag {epsilon}p decay (2004Mu30) and {sup 94}Ag p decay (2005Mu15, 2005Mu30), respectively. The half-life of the Zr member of this chain is of particular interest because of {sup 93}Zr's large contribution to long-term activity of nuclear reactor waste and also due to its potential as a supernova chronometer. During 2010, two new well-documented measurements of T{sub 1/2}({sup 93}Zr) were published (2010Ya01 and 2010Ca01); one agrees well with an earlier, undocumented measurement but, unfortunately, the other is many standard deviations lower for reasons which are not immediately apparent.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2012

Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C 5 H 5 )(Ox R ) 2 ] [Ox R = Ox 4S-iPr,Me2 , Ox 4R-iPr,Me2 , Ox 4S-tBu] . These optically active proligands react with an equivalent of M(NMe 2 ) 4 (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C 5 H 4 )(Ox R ) 2 }M(NMe 2 ) 2 in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C-N/C-H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C 5 H 4 )(Ox4 S-iPr,Me2 ) 2 }Zr(NMe 2 ) 2 ({S-2}Zr(NMe 2 ) 2 ) displays highest activity and enantioselectivity. Interestingly, S-2 Zr(NMe 2 ) 2 also desymmetrizes olefin moieties of achiral non-conjugated aminodienes and aminodiynes during cyclization. The cyclization of aminodienes catalyzed by S-2 Zr(NMe 2 ) 2 affords diastereomeric mixture of cis and trans cylic amines with high diasteromeric ratios and excellent enantiomeric excesses. Similarly, the desymmetrization of alkyne moieties in S-2 Zr(NMe 2 ) 2 -catalyzed cyclization of aminodiynes provides corresponding cyclic imines bearing quaternary stereocenters with enantiomeric excesses up to 93%. These stereoselective desymmetrization reactions are significantly affected by concentration of the substrate, temperature, and the presence of a noncyclizable primary amine. In addition, both the diastereomeric ratios and enantiomeric excesses of the products are markedly enhanced by N-deuteration of the substrates. Notably, the cationic zirconium-monoamide complex [ S-2 Zr(NMe 2 )][B(C 6 F 5 ) 4 ] obtained from neutral S-2 Zr(NMe 2 ) 2 cyclizes primary aminopentenes providing pyrrolidines with S-configuration; whereas S-2 Zr(NMe 2 ) 2 provides R-configured pyrrolidines. The yttrium complex S-2 YCH 2 SiMe 3 also affords S-configured pyrrolidines by cyclization of aminopentenes, however the enantiomeric excesses of products are low. An alternative optically active yttrium complex {PhB(C 5 H 4 )(Ox 4S-tBu ) 2 }YCH 2 SiMe 3 ({S-3}YCH 2 SiMe 3 ) is synthesized, which displays highly enantioselective in the cyclization of aminoalkenes at room temperature affording S-configured cyclic amines with enantiomeric excesses up to 96%. A noninsertive mechanism involving a six-membered transition state by a concerted C-N bond formation and N-H bond cleavage is proposed for {S-3}YCH 2 SiMe 3 system based on the kinetic, spectroscopic, and stereochemical features. In the end, a series of bis- and tris(oxazolinyl)borato iridium and rhodium complexes are synthesized with bis(oxazolinyl)phenylborane [PhB(Ox Me2 ) 2 ] n , tris(oxazolinyl)borane [B(Ox M ) 3 ]n, and tris(4,4-dimethyl-2-oxazolinyl)phenylborate [To M ] - . All these new and other known rhodium and iridium complexes were examined in acceptorless dehydrogenative decarbonylation of primary alcohols. The catalysts survey shows that the compound To M Ir(η 4 - C 8 H 12 ) is the most active for the conversion of primary alcohols into alkane, H 2 , and CO at 180 °C in toluene. Several aliphatic and aromatic primary alcohols are decarbonylated in the catalytic conditions. Furthermore, To M Ir(η 4 -C 8 H 12 ) is also able to decarbonylate polyols such as ethylene glycol and glycerol to syngas (H 2 and CO) at 180 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗