Stoichiometric analysis of compositionally graded combinatorial amorphous thin film oxides using laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) is a recently developed locally destructive elemental analysis technique that can be used to analyze solid, liquid, and gaseous samples. In the system explored here, a neodymium-doped yttrium aluminum garnet laser ablates a small amount of the sample and spectral emission from the plume is analyzed using a set of synchronized spectrometers. We explore the use of LIBS to map the stoichiometry of compositionally graded amorphous indium zinc oxide thin-film libraries. After optimization of the experimental parameters (distance between lens and samples, spot size on the samples, etc.), the LIBS system was calibrated against inductively coupled plasma atomic emission spectroscopy which resulted in a very consistent LIBS-based elemental analysis. Various parameters that need to be watched closely in order to produce consistent results are discussed. We also compare LIBS and x-ray fluorescence as techniques for the compositional mapping of libraries.

Solution synthesis and characterization of indium-zinc formate precursors for transparent conducting oxides.

A series of In-Zn formate mixtures were investigated as potential precursors to amorphous In-Zn-oxide (IZO) for transparent conducting oxide (TCO) applications. These mixtures were prepared by neutralization from formic acid and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and thermogravimetry-differential scanning calorimetry (TG-DSC) measurements. Thermal analysis revealed that a mixture of In and Zn formates reduced the overall decomposition temperature compared to the individual constituents and that OH-substitution enhanced the effect. In terms of precursor feasibility, it was demonstrated that the decomposition products of In-Zn formate could be directed toward oxidation or reduction by controlling the decomposition atmosphere or with solution acid additives. For TCO applications, amorphous IZO films were prepared by ultrasonic spray deposition from In-Zn formate solutions with annealing at 300-400 degrees C.

Using ligand bite angles to control the hydricity of palladium diphosphine complexes.

A series of [Pd(diphosphine)(2)](BF(4))(2) and Pd(diphosphine)(2) complexes have been prepared for which the natural bite angle of the diphosphine ligand varies from 78 degrees to 111 degrees. Structural studies have been completed for 7 of the 10 new complexes described. These structural studies indicate that the dihedral angle between the two planes formed by the two phosphorus atoms of the diphosphine ligands and palladium increases by over 50 degrees as the natural bite angle increases for the [Pd(diphosphine)(2)](BF(4))(2) complexes. The dihedral angle for the Pd(diphosphine)(2) complexes varies less than 10 degrees for the same range of natural bite angles. Equilibrium reactions of the Pd(diphosphine)(2) complexes with protonated bases to form the corresponding [HPd(diphosphine)(2)](+) complexes were used to determine the pK(a) values of the corresponding hydrides. Cyclic voltammetry studies of the [Pd(diphosphine)(2)](BF(4))(2) complexes were used to determine the half-wave potentials of the Pd(II/I) and Pd(I/0) couples. Thermochemical cycles, half-wave potentials, and measured pK(a) values were used to determine both the homolytic ([HPd(diphosphine)(2)](+) --> [Pd(diphosphine)(2)](+) + H*) and the heterolytic ([HPd(diphosphine)(2)](+) --> [Pd(diphosphine)(2)](2+) + H(-)) bond-dissociation free energies, Delta G(H*)* and Delta G(H-)*, respectively. Linear free-energy relationships are observed between pK(a) and the Pd(I/0) couple and between Delta G(H-)* and the Pd(II/I) couple. The measured values for Delta G(H*)* were all 57 kcal/mol, whereas the values of Delta G(H-)* ranged from 43 kcal/mol for [HPd(depe)(2)](+) (where depe is bis(diethylphosphino)ethane) to 70 kcal/mol for [HPd(EtXantphos)(2)](+) (where EtXantphos is 9,9-dimethyl-4,5-bis(diethylphosphino)xanthene). It is estimated that the natural bite angle of the ligand contributes approximately 20 kcal/mol to the observed difference of 27 kcal/mol for Delta G(H-)*.

Hydricities of BzNADH, CH5Mo(PMe3)(CO)2H, and C5Me5Mo(PMe3)(CO)2H in acetonitrile.

The thermodynamic hydride donor abilities of 1-benzyl-1,4-dihydronicotinamide (BzNADH, 59 +/- 2 kcal/mol), C(5)H(5)Mo(PMe(3))(CO)(2)H (55 +/- 3 kcal/mol), and C(5)Me(5)Mo(PMe(3))(CO)(2)H (58 +/- 2 kcal/mol) have been measured in acetonitrile by calorimetric and/or equilibrium methods. The hydride donor abilities of BzNADH and C(5)H(5)Mo(PMe(3))(CO)(2)H differ by 13 and 24 kcal/mol, respectively, from those reported previously for these compounds in acetonitrile. These results require significant revisions of the hydricities reported for related NADH analogues and metal hydrides. These compounds are moderate hydride donors as compared to previously determined compounds.

[Ni(Et2PCH2NMeCH2PEt2)2]2+ as a functional model for hydrogenases.

The reaction of Et(2)PCH(2)N(Me)CH(2)PEt(2) (PNP) with [Ni(CH(3)CN)(6)](BF(4))(2) results in the formation of [Ni(PNP)(2)](BF(4))(2), which possesses both hydride- and proton-acceptor sites. This complex is an electrocatalyst for the oxidation of hydrogen to protons, and stoichiometric reaction with hydrogen forms [HNi(PNP)(PNHP)](BF(4))(2), in which a hydride ligand is bound to Ni and a proton is bound to a pendant N atom of one PNP ligand. The free energy associated with this reaction has been calculated to be -5 kcal/mol using a thermodynamic cycle. The hydride ligand and the NH proton undergo rapid intramolecular exchange with each other and intermolecular exchange with protons in solution. [HNi(PNP)(PNHP)](BF(4))(2) undergoes reversible deprotonation to form [HNi(PNP)(2)](BF(4)) in acetonitrile solutions (pK(a) = 10.6). A convenient synthetic route to the PF(6)(-) salt of this hydride involves the reaction of PNP with Ni(COD)(2) to form Ni(PNP)(2), followed by protonation with NH(4)PF(6). A pK(a) of value of 22.2 was measured for this hydride. This value, together with the half-wave potentials of [Ni(PNP)(2)](BF(4))(2), was used to calculate homolytic and heterolytic Ni-H bond dissociation free energies of 55 and 66 kcal/mol, respectively, for [HNi(PNP)(2)](PF(6)). Oxidation of [HNi(PNP)(2)](PF(6)) has been studied by cyclic voltammetry, and the results are consistent with a rapid migration of the proton from the Ni atom of the resulting [HNi(PNP)(2)](2+) cation to the N atom to form [Ni(PNP)(PNHP)](2+). Estimates of the pK(a) values of the NiH and NH protons of these two isomers indicate that proton migration from Ni to N should be favorable by 1-2 pK(a) units. Cyclic voltammetry and proton exchange studies of [HNi(depp)(2)](PF(6)) (where depp is Et(2)PCH(2)CH(2)CH(2)PEt(2)) are also presented as control experiments that support the important role of the bridging N atom of the PNP ligand in the proton exchange reactions observed for the various Ni complexes containing the PNP ligand. Similarly, structural studies of [Ni(PNBuP)(2)](BF(4))(2) and [Ni(PNP)(dmpm)](BF(4))(2) (where PNBuP is Et(2)PCH(2)N(Bu)CH(2)PEt(2) and dmpm is Me(2)PCH(2)PMe(2)) illustrate the importance of tetrahedral distortions about Ni in determining the hydride acceptor ability of Ni(II) complexes.

Measurement of the hydride donor abilities of [HM(diphosphine)2]+ complexes (M = Ni, Pt) by heterolytic activation of hydrogen.

[M(diphosphine)2]2+ complexes (where M = Ni and Pt) react with hydrogen in the presence of bases to form the corresponding hydrides, [HM(diphosphine)2]+. In seven cases, equilibria have been observed from which the hydride donor ability (DeltaGdegrees(H-)) of the hydrides can be calculated. For six of these complexes, the DeltaGdegrees(H-) values calculated using heterolytic activation of hydrogen are compared with those based on thermodynamic cycles using pK(a) measurements and electrochemical half-wave potentials. The agreement between these two methods is good (within 1 kcal/mol). The reactivity of the various [M(diphosphine)2]2+ complexes toward hydrogen parallels their measured hydride acceptor abilities.

Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes.

The hydride complex [Pt(dmpe)2H]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) reversibly transfers H- to the rhenium carbonyl complex [CpRe(PMe3)(NO)(CO)]+, giving the formyl CpRe(PMe3)(NO)(CHO). From the equilibrium constant for the hydride transfer (16.2), the DeltaGdegrees for the reaction was determined (-1.6 kcal/mol), as was the hydride-donating ability of the formyl (44.1 kcal/mol). The hydride-donating ability, DeltaGdegrees(H-), is defined as the energy required to release the hydride ion into solution by the formyl complex [i.e. M(CHO) right arrow M(CO)+ + H-]. Subsequently, the hydride-donating ability of a series of formyl complexes was determined, ranging from 44 to 55 kcal/mol. With use of this information, two rhenium carbonyl complexes, [CpRe(NO)(CO)2]+ and [Cp*Re(NO)(CO)2]+, were hydrogenated to formyls, employing [Pt(dmpp)2]2+ and Proton-Sponge. Finally, the E(1/2)(I/0) values for five rhenium carbonyl complexes were measured by cyclic voltammetry. Combined with the known DeltaGdegrees(H-) values for the complexes, the hydrogen atom donating abilities could be determined. These values were all found to be approximately 50 kcal/mol.