Drew Rutherford

Tissue disposition, excretion and metabolism of 2,2',4,4',6-pentabromodiphenyl ether (BDE-100) in male Sprague-Dawley rats.

The absorption, disposition, metabolism and excretion study of orally administered 2,2′,4,4′,6-pentabromodiphenyl ether (BDE-100) was studied in conventional and bile-duct cannulated male rats. In conventional rats, >70% of the radiolabelled oral dose was retained at 72 h, and lipophilic tissues were the preferred sites for disposition, i.e. adipose tissue, gastrointestinal tract, skin, liver and lungs. Urinary excretion of BDE-100 was very low (0.1% of the dose). Biliary excretion of BDE-100 was slightly greater than that observed in urine, i.e. 1.7% at 72 h, and glucuronidation of phenolic metabolites was suggested. Thiol metabolites were not observed in the bile as had been reported in other PBDE metabolism studies. Almost 20% of the dose in conventional male rats and over 26% in bile-duct cannulated rats was excreted in the faeces, mainly as the unmetabolized parent, although large amounts of non-extractable radiolabel were also observed. Extractable metabolites in faeces were characterized by mass spectrometry. Monohydroxylated pentabromodiphenyl ether metabolites were detected; mono- and di-hydroxylated metabolites with accompanying oxidative debromination were also observed as faecal metabolites. Tissue residues of [14C]BDE-100 in liver, gastrointestinal tract and adipose tissue contained only parent material. The majority of the 0–72-h biliary radioactivity was associated with an unidentified 79-kDa protein or to albumin.

Synthesis and Structural Characterization of Tetradentate (N2O2) Ligand Complexes of Zinc

The potentially tetradentate-N2O2 ligands, N,N′-bis (o-hydroxybenzyl)-1,2-diaminoethane (SaleanH4), N,N′-bis(o-hydroxybenzyl)-1,3-diaminopropane (SalpanH4), N,N′-bis(o-hydroxybenzyl)-1,4-diaminobutane (SalbanH4), N,N′-bis(o-hydroxybenzyl)-1-6-diaminohexane (SalhanH4), N,N′-bis(o-hydroxybenzyl)-1,2-diaminobenzene (SalophanH4), and N, N′-bis (o-hydroxybenzyl)-1,2-dimino-4,5-dimethylbenzene (SalomphanH4), have been synthesized and used to prepare the series of zinc complexes, [SaleanH2Zn]2 (1), [Salpan H2Zn]2 (2), [SalbanH2Zn]2 (3), [SalhanH2Zn]2 (4), [SalophanH2Zn]2 (5), and [Salomphan H2Zn]2 (6), Compounds (2) and (5) have been structurally characterized with single-crystal x-ray diffractometry. The molecules consist of oxygen-bridged zinc dimers. Unique structures for (5) were determined from crystals grown from MeOH (5a) and DMF (5b). The structures possess varying numbers of solvent molecules in the unit cell. Crystal Data: (2) Space Group P1 with a = 13.076(3) A, b = 13.137(3) A, c = 13.228 (3) A, α = ...

Tetradentate −N2O2 ligand complexes of Tin(II). X-ray crystal structure of [N,N′-(1,2-ethylene) bis (salicylaldamine)]tin(II), (SaleanH2Sn)

The tetradentate −N2O2 ligands, [N,N′-(1,2-ethylenebis(salicylaldamine)] (SaleanH4 (1), [N,N′-(1,3-propylene)bis(salicylaldamine)](SalpanH4 (2)and [N,N′-(1,2-phenylenebis(salicylaldamine)] (SalophanH4) 3, were used to prepare Sn(II) complexes that are monomeric (SaleanH2Sn (7), SalpanH2Sn (8)) and dimeric ([SalophanH2Sn]2) (9)). The structure of 7 was determined by single-crystal X-ray crystallography: orthorhombic, space pbcn with a = 19.849(4), b = 10.791(3), c = 18.559(5) A and Z = 8. Compounds 8 and 9 undergo transmetallation reactions with three equivalents of AlMe3 to produce the trimetallic derivatives, SalpanAlMe(Alme2)2 (10) and SalophanAlMe(AlMe2)2 (11).

SYNTHESIS, STRUCTURE AND REACTIVITY OF SalanH2-METAL COMPLEXES

Abstract The present work is an exploration into synthesis of complexes of general formula LH2M (where M = Mn, Fe, Cu, and Al). The results obtained for L = Salophan (M = Fe (1), Cu (2)); Salomphan (M = Mn (3), Fe(4), Cu(5); Salpan (M = Fe(6), Cu(7)) and L = Salean (M = AlCl) (8) are reported. When 8 is dissolved in MeOH, [SaleanH2AlOMe]2 (9) is formed. In MeOH, and in the presence of air, 1 and 4 undergo oxidation of both the ligand and metal (Fe(II) to Fe(III) to form the “half” Schiff base complexes, [SalophanHFeOMe]2 (10) and [SalomphanHFeOMe]2 (11). Compounds 9–11 were structurally characterized. Crystal Data: (9) C36H46Al2N4O7, Space Group P-1 (no. 2) with a = 7.536(1) A, b = 10.513(2)A, c = 11.997(2) A, α = 97.72(1), β = 94.040(10)°, γ = 102.73(1), V = 914.8(3) A3 and Z = 2. With 226 parameters refined on 1226 reflections having F>6.0[sgrave](F), the final R values were R = 0.0540 and Rw = 0.0565; (10), C46H46Fe2N4O8, Space Group P-1 (no. 2) with a = 9.400(2) A, b = 10.718(4) A, c = 12.354(3) A, α ...

Examination of dibenzyl aluminum and gallium azides as potential precursors to AlN and GaN

Abstract This publication summarizes our attempts to prepare precursor molecules of formula Bn2MN3-THF [where Bn=benzyl, M=Ga (3) and Al (8)] and to use them in the low-temperature synthesis of AlN and GaN. Compound 3 was prepared from Bn2GaCl-THF (2) and Me3SiN3. Compound 8 was obtained by a different route which requires the combination of Cl2AlN3 and BnMgCl in toluene. During the course of this work two new amides, [Bn2AlNMe2]2 (4) and Bn2AlN(SiMe3)2-THF (5) were prepared and structurally characterized by X-ray crystallography.

The Trimetallic Structural Motif in Group 13 Chemistry

Abstract In the context of this Comment, a trimetallic complex will be defined as one in which three group 13 metals are contained in one complex by either one or two multidentate ligands. This motif has been observed sporadically in the literature throughout the years. Up until the present work, however, this unique structural arrangement has not been the focus of a systematic study. This Comment will comprise a discussion of such complexes, focusing on those employing the Salan class of ligands. Members of the Salan class of tetradentate (-N2O2) ligand, N,N′-bis(o-hydroxybenzyl)-1,2-diaminoethane (SaleanH4), N,N′-bis(o-hydroxybenzyl)-1,3-diaminopropane (SalpanH4), N,N′-bis(o-hydroxybenzyl)-1,2-diaminobenzene (SalophanH4), N,N′-bis(o-hydroxybenzyl)-1,2-diamino(4,5-dimethyl)benzene (SalomphanH4), form unique, monomeric trimetallic complexes when combined with three equivalents of MR3 (where M = Al, Ga; R = Me, Et, iBu). The aluminum complexes form cis ligand complexes with Salpan, Salophan and Salomphan a...

Synthesis and Structural Characterization of Monomeric and Dimeric Aluminum Amides

The synthesis and structural characterization of a trialkylaluminum amine adduct, Me3AlNH2tBu (1), four dimeric aluminum primary amides, [Me2AlNHtBu]2 (2), [iBu2AlNHPh]2(3), [iBu2AlNH(2,6-iPr2)Ph]2 (4), [(Me3Si)2AlNHPh]2 (5) and a monomeric aluminium amide, Mes2AlN(SiMe3)2 (6) are reported. Compounds 2_5 contribute to the relatively small number of structurally characterized primary amido complexes of aluminium. Compound 6 is one of a few examples of a monomeric, three-coordinate dialkyl aliminum amide. Crystal data: (1): Monoclinic, P21, a = 6.405(1), b = 10.742(1), c = 8.421(1)A, β = 109.42(1)°, V = 546.41(12), Z = 2, with 671 refl. with F > 4.0 σF, R = 0.0451; (2): Monoclinic, P21/n, a = 6.798(1), b = 12.273(1), c = 10.900(1) A, β = 96.25(2)°, V = 904.0(2), Z = 4, with 867 refl. with F > 4.0 σF, R = 0.0568; (3): Triclinic, P-1, a = 9.393(1), b = 9.479(1), c = 10.891(1) A, α = 67.22(1), β = 68.10(1), γ = 61.57(1)°, V = 764.66(13), Z = 2, with 1602 refl. with F > 4.0 σF, R = 0.0464; (4): Monoclinic, P21/...

A new electrophilic alaninol synthon. A general route to oxazolidinones of D or (R)-2-amino alcohols from L-serine

A new electrophilic alaninol synthon, (S)-4-(4′-tolylsulfonyloxymethyl)oxazolidin-2-one, derived from serine, undergoes nucleophilic displacements with Gilman cuprates and/or Grignard/CuX reagents in high yield to provide (R)-4-substituted oxazolidinones.

Structural characterization of the unusual adduct complex Me2ButAl–NH[Li(thf)3](C6H3Pri2-2,6)

Addition of ButLi to [Me2AlNH(C6H3Pri2-2,6)]2 results in the formation of the surprisingly stable adduct, Me2ButAl–NH[Li(thf)3](C6H3Pri2-2,6).

NEW PRECURSORS TO GROUP 13 NITRIDES

In searching for ideal unimolecular precursors to group 13 nitrides we have begun examining two new classes of molecules having the formulae, RnM(tet)3−n (n = 0, 1,2) and Bn2MN3 (where M = Al, Ga; tet = 5-phenyl-lH-tetrazole, and Bn= benzyl). These may be anticipated to undergo low-temperature decompositions according to equations 1 and 2, respectively. The absence of carbon bonds to the nitrogen ultimately incorporated into the material, as well as the presence of excess nitrogen are viewed as particularly advantageous. Preliminary results focused on the formation of aluminum nitride are presented herein.