Electronic structure in five-coordinate complexes of nickel(II) with heavy-donor ligands

I.

Various studies designed to elucidate the electronic structure of the arsenic donor ligand, o-phenylenebisdimethylarsine (diarsine), have been carried out. The electronic spectrum of diarsine has been measured at 300 and 77˚K. Electronic spectra of the molecular complexes of various substituted organoarsines and phosphines with tetracyanoethylene have been measured and used to estimate the relative ionization potentials of these molecules.

Uv photolysis of arsines in frozen solution (96˚K) has yielded thermally labile, paramagnetic products. These include the molecular cations of the photolyzed compounds. The species (diars)⁺ exhibits hyper-fine splitting due to two equivalent ⁷⁵As(I=3/2) nuclei. Resonances due to secondary products are reported and assignments discussed.

Evidence is presented for the involvement of d-orbitals in the bonding of arsines. In (diars)⁺ there is mixing of arsenic “lone-pair” orbitals with benzene ring π-orbitals.

II.

Detailed electronic spectral measurements at 300 and 77˚K have been carried out on five-coordinate complexes of low-spin nickel(II), including complexes of both trigonal bipyramidal (TBP) and square pyramidal (SPY) geometry. TBP complexes are of the form NiLX⁺ (X=halide or cyanide,

L = Qƭ(CH₂)₃As(CH₃)₂]₃ or

P [hexagon - Q'CH₃] , Q = P, As,

Q’=S, Se).

The electronic spectra of these compounds exhibit a novel feature at low temperature. The first ligand field band, which is asymmetric in the room temperature solution spectrum, is considerably more symmetrical at 77˚K. This effect is interpreted in terms of changes in the structure of the complex.

The SPY complexes are of the form Ni(diars)₂X^z (X=CL, Br, CNS, CN, thiourea, NO₂, As). On the basis of the spectral results, the d-level ordering is concluded to be xy ˂ xz, yz ˂ z² ˂˂ x² - y². Central to this interpretation is identification of the symmetry-allowed ¹A₁ → ¹E (xz, yz → x² - y²) transition. This assignment was facilitated by the low temperature measurements.

An assignment of the charge-transfer spectra of the five-coordinate complexes is reported, and electronic spectral criteria for distinguishing the two limiting geometries are discussed.

The life of John Brainerd, the brother of David Brainerd, and his successor as missionary to the Indians of New Jersey ... By Rev. Thomas Brainerd.

http://name.umdl.umich.edu/ABB4262

Arthur Douglas : missionary on Lake Nyasa, the story of his life

http://www.archive.org/details/arthurdouglasmi00douguoft

MUSICAL THEATER AND THE CLASSICAL VOICE: CROSSOVER SINGING IN THE TWENTIETH CENTURY

This dissertation explores the transformation of opera comique (as represented by the opera Carmen) and the impact of verismo style (as represented by the opera La Boheme) upon the development of operetta, American musical theater and the resultant change in vocal style. Late nineteenth-century operetta called for a classically trained soprano voice with a clear vibrato. High tessitura and legato were expected although the quality of the voice was usually lighter in timbre. The dissertation comprises four programs that explore the transformation of vocal and compositional style into the current vocal performance practice of American musical theater. The first two programs are operatic roles and the last two are recital presentations of nineteenth- and twentieth- century operetta and musical theater repertoire. Program one, Carmen, was presented on July 26, 2007 at the Marshall Performing Arts Center in Duluth, MN where I sang the role of Micaela. Program two, La Boheme, was presented on May 24,2008 at Randolph Road Theater in Silver Spring, MD where I sang the role of Musetta. Program three, presented on December 2, 2008 and program four, presented on May 10, 2009 were two recitals featuring operetta and musical theater repertoire. These programs were heard in the Gildenhorn Recital Hall at the Clarice Smith Performing Arts Center in College Park, MD. Programs one and two are documented in a digital video format available on digital video disc. Programs three and four are documented in a digital audio format available on compact disc. All programs are accompanied by program notes also available in digital format.