@article {2610, title = {HL2[P(1,2-O(2)C(6)H4)(3)] (L = DMSO or DMF): A Convenient Proton Source with a Weakly Basic Phosphorus(V) Anion}, journal = {Organometallics}, volume = {28}, number = {15}, year = {2009}, note = {ISI Document Delivery No.: 476PYTimes Cited: 0Cited Reference Count: 114Siu, Paul W. Gates, Derek P.}, month = {Aug}, pages = {4491-4499}, type = {Review}, abstract = {Treating phosphorus pentachloride with catechol (3 equiv) followed by the addition of dimethylsulfoxide (DMSO) or dimethylformamide (DMF) affords isolable bronsted acids of tris- (o-phenylenedioxy)phosphate anion, [p(1,2-O2C6H4)(3)](-). Specifically. H(DMSO)(2)[P(1,2-O2C6H4)(3)] and H(DMF)(2)[P(1,2-O2C6H4)(3)] have been isolated as crystalline solids. The downfield shifts of the acidic proton in their H-1 NMR spectra are consistent with its expected high acidity. The molecular structures of H(DMSO)(2)[P(1,2-O2C6H4)(3)] and H(DMF)(2)[P(1,2-O2C6H4)(3)] reveal that the protons in each are O-bound by either DMSO (x2) or DMF (x2). The N-H stretching frequency for the Oct(3)NH[P(1,2-O2C6H4)(3)] ((V) over bar (N-H) =3129 cm(-1)) is identical to that observed for trioctylammonium tetrafluoroborate ((v) over bar (N-H) = 3129 cm(-1)), suggesting that the basicity of these two weakly coordinating anions is similar. A preliminary investigation of the effectiveness of H(DMF)(2)[p(1,2-O2C6H4] in the protonolysis of metal-alkyl bonds was undertaken. Treating (dppe) pdMe(2) [dppe = 1,2-bis(diphenylphosphino)ethane] with H(DMF)(2)[P(1,2-O2C6H4)(3)] affords either [(dppe)pd(NCMe)Me][P(1,2-O2C6H4)(3) (1:1 ratio) or [(dppe)pd(NCMe)(2)(][P(1,2-O2C6H4)(3)](2) (1:2 ratio), both of which are structurally characterized.}, keywords = {ALTERNATING COPOLYMERIZATION, ANIONS, CARBON-MONOXIDE, COORDINATING ANIONS, CRYSTAL-STRUCTURE, DIMETHYL-SULFOXIDE, MIGRATORY INSERTION, MOLECULAR-STRUCTURE, OLEFIN, PALLADIUM(II) COMPLEXES, POLYMERIZATION, SUPERWEAK}, isbn = {0276-7333}, url = {://000268455900036}, author = {Siu, P. W. and Gates, D. P.} } @article {2647, title = {Reversible Orthopalladation of Phosphinimine-Imine Dichloropalladium(II) Complexes}, journal = {Organometallics}, volume = {28}, number = {13}, year = {2009}, note = {ISI Document Delivery No.: 466WHTimes Cited: 5Cited Reference Count: 26Wallis, Christopher J. Kraft, Ira L. Murphy, Jeffrey N. Patrick, Brian O. Mehrkhodavandi, Parisa}, month = {Jul}, pages = {3889-3895}, type = {Article}, abstract = {The synthesis and characterization of triphenylphosphinimine-arylimine bidentate ligands (aryl = 2,4,6-trimethylphenyl or 4-methylphenyl) along with their dichloropalladium(II) complexes are reported. These complexes form tridentate orthopalladated species upon heating in the presence or sodium acetate. The reverse reaction occurs upon addition of HCl center dot Et2O. The rate of orthopalladation and reprotonation is highly dependent on the steric bulk of the ligand. Related cationic species were also synthesized and characterized and found to be inert in the presence of 1-hexene and styrene.}, keywords = {1, 2-DIIMINOPHOSPHORANES, BEHAVIOR, CYCLOPALLADATION, ETHYLENE OLIGOMERIZATION CATALYSTS, IMINOPHOSPHORANES, LIGANDS, PALLADIUM(II) COMPLEXES, PD}, isbn = {0276-7333}, url = {://000267694100046}, author = {Wallis, C. J. and Kraft, I. L. and Murphy, J. N. and Patrick, B. O. and Mehrkhodavandi, Parisa} } @article {2168, title = {The complexes: RhCl(P-N)(THP), where P-N is P,N-chelated o-diphenylphosphino-N,N-dimethylaniline and THP is tris(hydroxymethyl)phosphine, and RhCl[(O)P-N][THP(O)] containing O-bonded phosphine oxides}, journal = {Inorganica Chimica Acta}, volume = {361}, number = {11}, year = {2008}, note = {ISI Document Delivery No.: 323VATimes Cited: 3Cited Reference Count: 42Lorenzini, Fabio Patrick, Brian O. James, Brian R.}, month = {Jul}, pages = {3199-3204}, type = {Article}, abstract = {{The complex RhCl(P-N)(THP) (1) is synthesized under argon from RhCl(cod)(THP) and P-N, and is structurally characterized; P-N = P, N-chelated o-diphenylphosphino-N,N-dimethylaniline}, keywords = {BEARING O-N, BIDENTATE PHOSPHINES, CATALYTIC-OXIDATION, HYDROFORMYLATION, LIGANDS, LOW-TEMPERATURE, N-DIMETHYLANILINYL SUBSTITUENTS, OXIDATION, PALLADIUM(II) COMPLEXES, phosphanes, phosphine oxides, phosphines, REACTIVITY, RHODIUM COMPLEXES, RHODIUM(I) COMPLEXES, X-ray structure}, isbn = {0020-1693}, url = {://000257475300029}, author = {Lorenzini, F. and Patrick, B. O. and James, Brian R.} } @article {1267, title = {Carbohydrate-appended 2,2 {\textquoteright}-dipicolylamine metal complexes as potential imaging agents}, journal = {Inorganic Chemistry}, volume = {44}, number = {8}, year = {2005}, note = {ISI Document Delivery No.: 916GWTimes Cited: 44Cited Reference Count: 58}, month = {Apr}, pages = {2698-2705}, type = {Article}, abstract = {Three discrete carbohydrate-appended 2,2{\textquoteright}-dipicolylamine ligands were complexed to the {M(CO)3}(+) (M = Tc-99m/ Re) core: 2-(bis(2-pyridinylmethyl)amino)ethyl-beta-D-glucopyranoside (L-1), 2-(bis(2-pyridinylmethyl)amino)ethyl-beta-Dxylopyranoside (L-2), and 2-(bis(2-pyridinylmethyl)amino)ethyl-alpha-D-mannopyranoside (L-3). An ethylene spacer is used to separate the carbohydrate moiety and the dipicolylamine (DPA) function in all three ligands. The Re complexes [Re(L1-3)(CO)(3)]Br were characterized by H-1 and C-13 1D/2D NMR spectroscopies, which confirmed the pendant nature of the carbohydrate moieties in solution. NMR measurements also established the long-range asymmetric effect of the carbohydrate functions on the chelating portion of the ligand. One analogue, [Re(L-1)(CO)(3)]Cl, was characterized in the solid state by X-ray crystallography. Further characterization was provided by IR spectroscopy, elemental analysis, conductivity, and mass spectrometry. Radiolabeling of L-1-L-3 with [Tc-99m(H2O)(3)(CO)(3)](+) afforded high yield compounds of identical character to the Re analogues. The radiolabeled compounds were found to be stable toward ligand exchange in the presence of a large excess of either cysteine or histidine over a 24-h period.}, keywords = {AMINO-SUGARS, ANTITUMOR-ACTIVITY, BOMBESIN ANALOG, D-GLUCOSE, HIGH-AFFINITY, IN-VITRO, LIGANDS, PALLADIUM(II) COMPLEXES, RHENIUM CARBONYL-COMPLEXES, STRUCTURAL-CHARACTERIZATION, TRIDENTATE}, isbn = {0020-1669}, url = {://000228374400020}, author = {Storr, T. and Sugai, Y. and Barta, C. A. and Mikata, Y. and Adam,Michael J. and Yano, S. and Orvig, Chris} } @article {1267, title = {Carbohydrate-appended 2,2 {\textquoteright}-dipicolylamine metal complexes as potential imaging agents}, journal = {Inorganic Chemistry}, volume = {44}, number = {8}, year = {2005}, note = {ISI Document Delivery No.: 916GWTimes Cited: 44Cited Reference Count: 58}, month = {Apr}, pages = {2698-2705}, type = {Article}, abstract = {Three discrete carbohydrate-appended 2,2{\textquoteright}-dipicolylamine ligands were complexed to the {M(CO)3}(+) (M = Tc-99m/ Re) core: 2-(bis(2-pyridinylmethyl)amino)ethyl-beta-D-glucopyranoside (L-1), 2-(bis(2-pyridinylmethyl)amino)ethyl-beta-Dxylopyranoside (L-2), and 2-(bis(2-pyridinylmethyl)amino)ethyl-alpha-D-mannopyranoside (L-3). An ethylene spacer is used to separate the carbohydrate moiety and the dipicolylamine (DPA) function in all three ligands. The Re complexes [Re(L1-3)(CO)(3)]Br were characterized by H-1 and C-13 1D/2D NMR spectroscopies, which confirmed the pendant nature of the carbohydrate moieties in solution. NMR measurements also established the long-range asymmetric effect of the carbohydrate functions on the chelating portion of the ligand. One analogue, [Re(L-1)(CO)(3)]Cl, was characterized in the solid state by X-ray crystallography. Further characterization was provided by IR spectroscopy, elemental analysis, conductivity, and mass spectrometry. Radiolabeling of L-1-L-3 with [Tc-99m(H2O)(3)(CO)(3)](+) afforded high yield compounds of identical character to the Re analogues. The radiolabeled compounds were found to be stable toward ligand exchange in the presence of a large excess of either cysteine or histidine over a 24-h period.}, keywords = {AMINO-SUGARS, ANTITUMOR-ACTIVITY, BOMBESIN ANALOG, D-GLUCOSE, HIGH-AFFINITY, IN-VITRO, LIGANDS, PALLADIUM(II) COMPLEXES, RHENIUM CARBONYL-COMPLEXES, STRUCTURAL-CHARACTERIZATION, TRIDENTATE}, isbn = {0020-1669}, url = {://000228374400020}, author = {Storr, T. and Sugai, Y. and Barta, C. A. and Mikata, Y. and Adam,Michael J. and Yano, S. and Orvig, Chris} } @article {1266, title = {Novel carbohydrate-appended metal complexes for potential use in molecular imaging}, journal = {Chemistry-a European Journal}, volume = {11}, number = {1}, year = {2005}, note = {ISI Document Delivery No.: 887BZTimes Cited: 27Cited Reference Count: 60}, month = {Dec}, pages = {195-203}, type = {Article}, abstract = {Seven discrete sugar-pendant diamines were complexed to the {M(CO)(3)}(+) (Tc-99m/Re) core: 1,3-diamino-2-propyl beta-D-glucopyranoside (L-1), 1,3-diamino-2-propyl beta-D-xylopyranoside (L-2), 1,3-diamino-2-propyl alpha-D-mannopyranoside (L-3), 1,3-diamino-2-propyl alpha-D-galactopyranoside (L-4), 1,3diamino-2-propyl beta-D-galactopyranoside (L-5), 1,3-diamino-2-propyl beta-(alpha-D-glucopyranosyl-(1,4)-D-glucopyrano- side) (L-6), and bis(aminomethyl)bis[(beta-D-glucopyranosyloxy)methyl]methane (L-7). The Re complexes [Re((LL7)-L-1)(Br)(CO)(3)] were characterized by H-1 and C-13 1D/2D NMR spectroscopy which confirmed the pendant nature of the carbohydrate moieties in solution. Additional characterization was provided by IR spectroscopy, elemental analysis, and mass spectrometry. Two analogues, [Re(L-2)(CO)(3)Br] and [Re(L-3)(CO)(3)Br], were characterized in the solid state by X-ray crystallography and represent the first reported structures of Re organometallic carbohydrate compounds. Conductivity measurements in H2O established that the complexes exist as [Re(L-1-L-7)- (H2O)(CO)(3)]Br in aqueous conditions. Radiolabelling of V-L 7 with [Tc-99m(H2O)(3)(CO)(3)](+) afforded in high yield compounds of identical character to the Re analogues. The radiolabelled compounds were determined to exhibit high in vitro stability towards ligand exchange in the presence of an excess of either cysteine or histidine over a 24 h period.}, keywords = {AMINO-SUGARS, ANTITUMOR-ACTIVITY, carbohydrates, CRYSTAL-STRUCTURES, D-GLUCOSE, HIGH-AFFINITY, IN-VITRO, molecular imaging, PALLADIUM(II) COMPLEXES, RADIOPHARMACEUTICALS, rhenium, STRUCTURAL-CHARACTERIZATION, SUGAR-PENDANT, TC-99M, technetium}, isbn = {0947-6539}, url = {://000226278700018}, author = {Storr, T. and Obata, M. and Fisher, C. L. and Bayly, S. R. and Green, D. E. and Brudzinska, I. and Mikata, Y. and Patrick, B. O. and Adam,Michael J. and Yano, S. and Orvig, Chris} } @article {1266, title = {Novel carbohydrate-appended metal complexes for potential use in molecular imaging}, journal = {Chemistry-a European Journal}, volume = {11}, number = {1}, year = {2005}, note = {ISI Document Delivery No.: 887BZTimes Cited: 27Cited Reference Count: 60}, month = {Dec}, pages = {195-203}, type = {Article}, abstract = {Seven discrete sugar-pendant diamines were complexed to the {M(CO)(3)}(+) (Tc-99m/Re) core: 1,3-diamino-2-propyl beta-D-glucopyranoside (L-1), 1,3-diamino-2-propyl beta-D-xylopyranoside (L-2), 1,3-diamino-2-propyl alpha-D-mannopyranoside (L-3), 1,3-diamino-2-propyl alpha-D-galactopyranoside (L-4), 1,3diamino-2-propyl beta-D-galactopyranoside (L-5), 1,3-diamino-2-propyl beta-(alpha-D-glucopyranosyl-(1,4)-D-glucopyrano- side) (L-6), and bis(aminomethyl)bis[(beta-D-glucopyranosyloxy)methyl]methane (L-7). The Re complexes [Re((LL7)-L-1)(Br)(CO)(3)] were characterized by H-1 and C-13 1D/2D NMR spectroscopy which confirmed the pendant nature of the carbohydrate moieties in solution. Additional characterization was provided by IR spectroscopy, elemental analysis, and mass spectrometry. Two analogues, [Re(L-2)(CO)(3)Br] and [Re(L-3)(CO)(3)Br], were characterized in the solid state by X-ray crystallography and represent the first reported structures of Re organometallic carbohydrate compounds. Conductivity measurements in H2O established that the complexes exist as [Re(L-1-L-7)- (H2O)(CO)(3)]Br in aqueous conditions. Radiolabelling of V-L 7 with [Tc-99m(H2O)(3)(CO)(3)](+) afforded in high yield compounds of identical character to the Re analogues. The radiolabelled compounds were determined to exhibit high in vitro stability towards ligand exchange in the presence of an excess of either cysteine or histidine over a 24 h period.}, keywords = {AMINO-SUGARS, ANTITUMOR-ACTIVITY, carbohydrates, CRYSTAL-STRUCTURES, D-GLUCOSE, HIGH-AFFINITY, IN-VITRO, molecular imaging, PALLADIUM(II) COMPLEXES, RADIOPHARMACEUTICALS, rhenium, STRUCTURAL-CHARACTERIZATION, SUGAR-PENDANT, TC-99M, technetium}, isbn = {0947-6539}, url = {://000226278700018}, author = {Storr, T. and Obata, M. and Fisher, C. L. and Bayly, S. R. and Green, D. E. and Brudzinska, I. and Mikata, Y. and Patrick, B. O. and Adam,Michael J. and Yano, S. and Orvig, Chris} } @article {407, title = {Homo- and heterobimetallic precursor catalysts for the Heck reaction, and a proposal for a general catalytic cooperativity index}, journal = {Advanced Synthesis \& Catalysis}, volume = {344}, number = {10}, year = {2002}, note = {ISI Document Delivery No.: 629XZTimes Cited: 22Cited Reference Count: 58}, month = {Dec}, pages = {1126-1134}, type = {Article}, abstract = {Homo- (Pd-2) and heterobimetallic (PtPd) complexes supported by a P,P-bridging, bis(P,N-chelating) coordination mode of the potentially hexadentate ligand 1,1-bis[di(o-N,N-dimethylanilinyl)phosphino] methane (dmapm) are effective catalyst precursors for the aerobic Heck coupling of iodobenzene and styrene at 100degreesC in DMF/H2O solution containing K2CO3. This medium allows for trivial separation of the trans-stilbene product which precipitates after the reaction mixture is cooled. The bimetallic precursors are more active than predicted from the sum of the activities of complexes chosen to mimic their mono-metallic "half units," suggesting some degree of intermetallic cooperativity during the reaction. A non-linear dependence of initial rate on catalyst concentration implies, however, that the complexes do not remain intact, and may be involved in dissociative equilibria with non-dmapm containing monometallic components that are more active species for the Heck coupling. The complexes are slowly degraded by oxidation at a phosphorus centre. A general index for quantifying the degree of intermetallic cooperativity during a catalytic cycle is proposed and its utility and limitations are discussed.}, keywords = {aerobic), ASYMMETRIC CATALYSIS, bimetallic, CHEMISTRY, cooperativity, COORDINATION, COUPLING, Heck reaction (aqueous, HIGH REGIOSELECTIVITY, homogeneous, HYDROFORMYLATION, HYDROGEN, LIGANDS, NICKEL(II) SITE, palladium, PALLADIUM(II) COMPLEXES, phosphine (anilinyl), platinum, REACTIONS, thermomorphic, VINYLIC SUBSTITUTION-REACTIONS}, isbn = {1615-4150}, url = {://000180078900015}, author = {Jones, N. D. and James, Brian R.} }