Papers by Marilyn Olmstead
Acta crystallographica. Section C, Structural chemistry, 2015
The reaction of the proton-transfer compound piperazine-1,4-diium pyrazine-2,3-dicarboxylate 4.5-... more The reaction of the proton-transfer compound piperazine-1,4-diium pyrazine-2,3-dicarboxylate 4.5-hydrate, C4H12N2(2+)·C6H2N2O4(2-)·4.5H2O or (pipzH2)(pyzdc)·4.5H2O (pyzdcH2 is pyrazine-2,3-dicarboxylic acid and pipz is piperazine), (I), with Zn(NO3)2·6H2O and CoCl2·6H2O results in the formation of bis(piperazine-1,4-diium) bis(μ-pyrazine-2,3-dicarboxylato)-κ(3)N(1),O(2):O(3);κ(3)O(3):N(1),O(2)-bis[aqua(pyrazine-2,3-dicarboxylato-κ(2)N(1),O(2))zinc(II)] decahydrate, (C4H12N2)2[Zn2(C6H2N2O4)4(H2O)2]·10H2O or (pipzH2)2[Zn(pyzdc)2(H2O)]2·10H2O, (II), and catena-poly[piperazine-1,4-diium [cobalt(II)-bis(μ-pyrazine-2,3-dicarboxylato)-κ(3)N(1),O(2):O(3);κ(3)O(3):N(1),O(2)] hexahydrate], {(C4H12N2)[Co(C6H2N2O4)2]·6H2O}n or {(pipzH2)[Co(pyzdc)2]·6H2O}n, (III), respectively. In (I), pyzdcH2 is doubly deprotonated on reaction with piperazine as a base. Compound (II) crystallizes as a dimer, whereas compound (III) exists as a one-dimensional coordination polymer. In (II), two pyzdc(2-) groups c...
Inorganic Chemistry, 1995
The synthesis and structural characterization of the linear bis(catecho1) amide ligand, N,N'-bis(... more The synthesis and structural characterization of the linear bis(catecho1) amide ligand, N,N'-bis(2,3-dihydroxybenzoyl)-l,7-diazaheptane (5-LICAM, 11, was studied along with several metal complexes, namely, Ni2+ and Co2+. We were able to obtain a single-crystal X-ray analysis of a derivative of 1, the hemimethoxy ligand, 5-LICAM(OCH3)2, 2, where partial demethylation of the fully methylated derivative of 1 was serendipitiously obtained in the presence of a deficiency of BBr3. The X-ray structure showed why we retained the methoxy group, during the partial demethylation reaction, in each catechol amide ring by the fact that a selective intramolecular hydrogen bond occurs between the one demethylated OH group in each catechol ring and the amide carbonyl in the adjacent position (C=O---HO, 1.67 A). Reaction of 1 with a Ni2+ salt provided the first structurally characterized square planar, linear bis-catechol amide, dianionic metal complex, with cesium as the counterion, CS~[~-LICAM-N~]*~DMF, 3, (Ni-0, 1.87 A, 0-Ni-0, 87.9-92.5'). It is also interesting to note that one of the cesium atoms was cis-bonded to the catechol oxygens in each ring (02---Csl, 06-Csl = 3.23 A, 3.03 A) and to the carbonyl oxygen of one of the three DMF solvent molecules (Csl-O=C, 3.13 A), while the other cesium atom was bonded to all three carbonyl oxygens of the DMF molecules in the structure (Cs2-0 7 , 0 8 = 3.13, 3.12 A). A Co2+ analogue of 3, Cs2[5-LICAM-Co]*DMF, 4, provided a similar structure as ascertained by FT-IR, FABMS, and elemental analysis. In order to test the utilization of 1 in removing Ni2+ from aqueous solution for environmental inorganic applications, we synthesized the polymer pendant ligand version, PS-5-LICAM, bonded to modified 6% macroporous divinylbenzene-polystyrene beads (0.55 mmol/g), with an important modification of a sulfonate group on the catechol ring, PS-5-LICAMS, to impart hydrophilicity to the ligand site. Indeed, we found that the PS-5-LICAMS ligand removed 0.35 m o l of Ni/g of polymer beads from aqueous solution at pH 2.5, but unfortunately, was not selective to Ni'+ in competition with other divalent metal
Inorganic Chemistry, 2002
Journal of The American Chemical Society, 2002
The reaction of Sn(Cl)C(6)H(3)-2,6-Dipp(2) (Dipp = C(6)H(3)-2,6-Pr(i)()(2)) with a stoichiometric... more The reaction of Sn(Cl)C(6)H(3)-2,6-Dipp(2) (Dipp = C(6)H(3)-2,6-Pr(i)()(2)) with a stoichiometric amount of potassium in benzene affords 2,6-Pr(i)()(2)-H(3)C(6)SnSnC(6)H(3)-2,6-Pr(i)()(2) (1) as dark blue-green crystals. The compound 1 is a tin analogue of an alkyne. It was characterized by (1)H and (13)C NMR and UV-vis spectroscopy, cyclic voltammetry, combustion analysis and X-ray crystallography. The structural data show that 1 has a trans-bent, planar C(ipso)SnSnC(ipso) skeleton with a Sn-Sn bond distance of 2.6675(4) A and a Sn-Sn-C angle of 125.24(7) degrees. The Sn-Sn distance, which is ca. 0.15 A shorter than a conventional Sn-Sn single bond, and the trans-bent structure indicate the presence Sn-Sn multiple bond character unlike the related singly bonded ArPbPbAr species.
Angewandte Chemie-international Edition, 2006
DFT Calculations. Full reference for Gaussian 03 program. Frisch, M. J.; Trucks, G. W.; Schlegel,... more DFT Calculations. Full reference for Gaussian 03 program. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K.N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Polyhedron, 2006
The reaction of the sterically hindered terphenol Ar∗OH(Ar∗=C6H3-2,6(C6H2-2,4,6-Pr3i)2) with trim... more The reaction of the sterically hindered terphenol Ar∗OH(Ar∗=C6H3-2,6(C6H2-2,4,6-Pr3i)2) with trimethylaluminum or trimethylgallium in ether led to the isolation of the corresponding ether-coordinated monophenoxide species Ar*OM(CH3)2(Et2O) (M=Al (1) or Ga (2)). The reaction of the lithium salt of the related bulky terphenol Ar′OH(Ar′=C6H3-2,6(C6H3-2,6-Pr3i)2) with the divalent species MCl2 (M=Ge, Sn) afforded the novel germanium (II) and tin (II) mono- and bisphenoxides
Inorganic Chemistry, 1993
Recent work1 has shown that it is possible to effect reduction of the tetraaryldigallium compound... more Recent work1 has shown that it is possible to effect reduction of the tetraaryldigallium compound TripzGaGaTrip2 (Trip = 2,4,6-i-Pr&Hz) with lithium powder in diethyl ether solution to give the salt 2]+[Trip2GaGaTrip2]'-, 1. This .-Trip Trip (Li(l2mwn-4)2]+ [ Tr; Ga-Ga : M ]
Journal of The American Chemical Society, 2007
Tetrahedron, 2006
The quenching of the anionic dye 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (pyranine)... more The quenching of the anionic dye 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (pyranine) with three different boronic acid-substituted benzyl viologens was determined, and the fluorescence signal modulation obtained upon addition of glucose to the dye/ quencher system was also studied. The benzyl viologen that contains boronic acids in the ortho-position (o-BBV) was found to display unique behavior, which can be rationalized by a charge neutralization mechanism facilitated by an intramolecular interaction between sp 3 boronate and the quaternary nitrogen of the viologen. Potentiometric titration and 11 B NMR spectroscopy were used to generate pH profiles for the boronic acids, which provide additional evidence for the proposed mechanism. Ó 2006 Elsevier Ltd. All rights reserved. higher pK a lower pK a Scheme 1. Equilibria between boronic acids and generic diols.
Journal of the American Chemical Society, 2015
The regioselective synthesis of easily isolable pure bismethano derivatives of C60 and C70 with h... more The regioselective synthesis of easily isolable pure bismethano derivatives of C60 and C70 with high steric congestion is described using 1,3-dibenzoylpropane bis-p-toluenesulfonyl hydrazone as the addend precursor. When the addition occurs at two [6,6] ring junctions within the same hexagon, bisadducts with mirror symmetry are obtained for both C60 and C70. When the addition occurs at two [5,6] ring junctions in C60, a symmetrical adduct is formed, which readily undergoes photo-oxygenation and ring opening to yield a fullerene with a hole in the cage. In this work, we also propose a simple and general system to name all of the possible [6,6] bisadduct isomers on C70.
Inorganic chemistry, Jan 10, 2015
New insight into the complexity of the reaction of the prominent catalyst RuCl2(PPh3)3 with carbo... more New insight into the complexity of the reaction of the prominent catalyst RuCl2(PPh3)3 with carbon disulfide has been obtained from a combination of X-ray diffraction and (31)P NMR studies. The red-violet compound originally formulated as a cationic π-CS2 complex, [RuCl(π-CS2)(PPh3)3]Cl, has been identified as a neutral molecule, RuCl2(S2CPPh3)(PPh3)2, which contains the unstable zwitterion S2CPPh3. In the absence of RuCl2(PPh3)3, there is no sign of a reaction between triphenylphosphine and carbon disulfide, although more basic trialkylphosphines form red adducts, S2CPR3. Despite the presence of an unstable ligand, RuCl2(S2CPPh3)(PPh3)2 is remarkably stable. It survives melting at 173-174 °C intact, is stable to air, and undergoes reversible electrochemical oxidation to form a monocation. When the reaction of RuCl2(PPh3)3 with carbon disulfide is conducted in the presence of methanol, crystals of orange [RuCl(S2CPPh3)(CS)(PPh3)2]Cl·2MeOH and yellow RuCl2(CS)(MeOH)(PPh3)2 also form....
Acta crystallographica. Section C, Crystal structure communications, 2006
The structures of three chiral vinyldioxazaborocanes are reported, namely (2E)- and (2Z)-6-benzyl... more The structures of three chiral vinyldioxazaborocanes are reported, namely (2E)- and (2Z)-6-benzyl-2-buten-2-yl-1,3,6,2-dioxazaborocane, C27H30BNO2, (II) and (III), respectively, and (2Z)-2-buten-2-yl-6-isobutyl-1,3,6,2-dioxazaborocane, C24H32BNO2, (IV). These compounds may be useful in asymmetric reactions. In the structures reported here, the N-B donor-acceptor bond is longer than in any previously reported analogous compounds.
Angewandte Chemie (International ed. in English), 2001
57), 121 (65); 'H N M R 6 0.9-1.1 (m, 12 H containing s at 1.08), 1. 2-2.1 (m, 12 H). or-Brominat... more 57), 121 (65); 'H N M R 6 0.9-1.1 (m, 12 H containing s at 1.08), 1. 2-2.1 (m, 12 H). or-Bromination of 85 mg (0.39 mmol) of 58 and the subsequent dehydrobromination as described above gave 73 mg (86% yield) of (~t ) -5 after flash chromatography (10% ether) whose spectral data (IR, 'H and 13C NMR) were identical with those of the natural p r o d~c t .~
... Complexes Alan L. Balch,* Yee Wai Chan, Marilyn Olmstead, and Mark W. Renner Contribution fro... more ... Complexes Alan L. Balch,* Yee Wai Chan, Marilyn Olmstead, and Mark W. Renner Contribution from the Department of Chemistry, University of California, Davis, California 9561 6. Received September IO, I984 ... (15) Guzy, CM; Raynor, J. B.; Symons, M. CR J. Chem. SOC. ...
Journal of The Chemical Society-perkin Transactions 2, 1990
Inorganic Chemistry, 1993
... Deborah M. Choquette,t Mary Jo Ti",? Jason L. Hobbs,t Thomas M. Nicholson,t Mari... more ... Deborah M. Choquette,t Mary Jo Ti",? Jason L. Hobbs,t Thomas M. Nicholson,t Marilyn M. Olmstead,* and Roy P. Planalp'~t ... 1972, B28, 1619. (17) Del Piero, G.; Cesari, M.; Dozzi, G.; Mazzei, A. J. Organomet. Chem. 1977, 129, 281. (18) Waggoner, KM; Power, PPJ Am. Chem. ...
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Papers by Marilyn Olmstead