A Pilot Survey of Vocal Health in Young Singers

The objective of this study was to determine the incidence of vocal problems in young choir singers and to correlate vocal problems with demographic and behavioral information. A questionnaire addressing vocal habits and hygiene was offered to 571 young choir singers, up to 25 years of age, who sing at least weekly; 129 (22.6%) responded. More than one-half of the respondents had experienced vocal difficulty, particularly older adolescents. Detrimental behaviors and circumstances surveyed were not reflective of the incidence of vocal difficulty, except for morning hoarseness, chronic fatigue, insomnia, and female gender after puberty. Voice care professionals should be aware that self-reported voice difficulties are common among young choral singers, especially postpubescent girls, and children with symptoms consistent with reflux (morning hoarseness) and emotional stress (insomnia). Laryngologists should communicate with choral conductors and singing teachers to enhance early identification and treatment of children with voice complaints, and to develop choral educational strategies that help decrease their incidence.     

The preparation and structure of 1,4,5,6,7,7-hexachloro-2-endo-ferrocenylhydroxymethyl-3-endo-hydroxymethyl-5-norbornene

The crystal structure of a novel ferrocene derivative with potential flame-retardant/smoke-suppressant activity, 1,4,5,6,7,7-hexachloro-2-endo-ferrocenyl-hydroxymethyl-3-endo-hydroxymethyl-5-norbornene, has been determined. Some of the carbon–carbon bonds within the chlorendic residue are unusually long, and there is no interaction between the hydroxyl groups and the iron atom. There is evidence of intramolecular hydrogen bonding between the two hydroxyl groups.     

Mixed nitrosyl/phosphinidene and nitrene/phosphinidene clusters of ruthenium

Reaction of the aminophosphinidene complex [Ru5(CO)15(mu 4-PNPri2)] 1 with [PPN][NO2] (PPN = Ph3P=N=PPh3) led to the mixed nitrosyl/phosphinidene cluster complex [PPN][Ru5(CO)13(mu-NO)(mu 4-PNPri2)] 2 which is transformed into the novel nitrene/phosphinidene cluster [Ru5(CO)10(mu-CO)2(mu 3-CO)(mu 4-NH)(mu 3-PNPri2)] 3 via treatment with triflic acid.     

Novel nucleophilic substitution of alkyl bromo-2(1H)-pyridones

Nucleophilic substitution of certain alkyl bromo-2(1H)-pyridones gave some unexpected products where the alkyl group is substituted and the ring bromine is replaced by hydrogen. The expected ring substituted product is also formed, but only as the minor product in most cases. Many reactions are cited with various nucleophiles, and a plausible mechanism is also presented.     

Reactivity patterns of thermally stable, terminal, electrophilic phosphinidene complexes towards diazoalkanes: oxidation at the phosphorus centre and formation of P-bound eta1-phosphaazine, eta1-phosphaalkene and eta3-diazaphosphaallene complexes

The thermally stable, terminal phosphinidene complexes [CpM(CO)2(eta1-PNiPr2)]AlCl4(Cp= Cp, Cp*; M = Fe) and [Cp*M(CO)3(eta1-PNiPr2)]AlCl4 (M = Cr, Mo, W) react with Ph2C=N=N to form terminal P-coordinated eta1-phosphaazine and eta3-diazaphosphaallene ligands, respectively, whereas [CpFe(CO)2(eta1-PNiPr2)]AlCl4 reacts with Me3SiCHN2 affording a terminal phosphorus bound eta1-phosphaalkene complex.     

σ,π-acetylido complexes via P---C bond cleavage of phosphinoacetylenes: X-ray structure of Fe2(CO)6(CCPh)(PPh2)

Solutions of Co^II salts of organic acids in primary amines absorb molecular oxygen rapidly and irreversibly forming μ-dioxygen—cobalt complexes. Thermolysis leads to a homopolar cleavage of the OO bond with subsequent radical reactions involving ligand amine. After thermolysis the capacity of oxygen uptake is reestablished (catalysis).     

Synthesis and structure of the cluster ion pair [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]]. A theoretical overview of M3(mu-PR2)3 frameworks

The compound [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]] (1), obtained via the addition of PCl(NPri2)2 to K2[Ru4(CO)13], crystallizes in the monoclinic space group P2l/c with a = 15.537(8) A, b = 36.151(16) A, c = 19.407(5) A, beta = 91.14(2) degrees, Z = 4, and R = 0.069 for 8006 observed reflections. The unit cell is unusual in that it contains both a typical octahedral Ru6 cluster anion (1a), featuring an encapsulated carbide, and a symmetrical phosphido bridge, in addition to a 50-electron trinuclear cluster cation [Ru3(CO)9[mu-P(NPri2)2]3]+ (1c). The latter, with approximate D3h symmetry, exhibits long Ru-Ru distances (> or = 3.15 A). Among the family of clusters with M3(mu-PR2)3 cores and different numbers of both electrons (TEC) and terminal ligands (LxLyLz), 1c is unique in that it is a 333 stereotype with 50 valence electrons. MO calculations permit us to predict the existence of redox congeners of 1c clusters and related 48e Re3 clusters. This work also presents a summary of the relationships between the electronic and the geometric structures for all known M3LxLyLz(mu-PR2)3 species. The basic stereochemical features are influenced by the total-electron count and, hence, by the degree of M-M bonding, as well as the remarkable flexibility of the phosphido bridging ligands. The mu-PR2 ligands need not necessarily lie in the M3 plane, and a wide range of M-P-M angles (as small as 72 degrees or as large as 133 degrees) have been observed.     

The selenium-mercury interaction: synthesis,spectroscopic and x-ray structural studies of methylmercury-selenourea complexes

The synthesis of selenium bound selenourea complexes of methylmercury, [CH₃HgSeC(NH₂)₂]X (X=Cl, Br, NO₃, ClO₄) are described. A single crystal X-Ray analysis of the nitrate salt has provided for the first time bond length data pertinent to the biologically important mercury-selenium interaction. Crystals of [CH₃HgSeC(NH₂)₂] NO₃ belong to the space group PnZic with a = 7.524(1), b = 11.204(2), c = 9.738(2)Å, and z = 4. The structure was solved and refined using 561 observed reflections measured on a Syntex P2₁ diffractometer to a final R value of 0.037. The mercury atom is linearly coordinated to the methyl group and the selenium atom of the selenourea with Hg-Se of 2.477(3)Å. Strong Hg-Se bonding is indicated by the X-Ray data and by the ¹H - ¹⁹⁹Hg nmr coupling constants. A comparison of spectroscopic data for analogous thio and selenourea complexes is presented.     

Coordination complexes of acetylenic phosphines and diphosphines

The reactions of π-cyclopentadienylnickel carbonyl dimer with 3,3,3-trimethylpropynyldiphenylphosphine and phenylethynyldiphenylphosphine are described. The products have been characterized by elemental and mass spectral analysis, infrared and NMR spectroscopy. An acetylene bridged complex (π-C₅H₅Ni)₂Ph₂PC₂-t-Bu, containing an uncoordinated phosphorus atom, has been prepared. The complex can be oxidized to the phosphine oxide derivative (π-C₅H₅Ni)₂Ph₂P(O)C₂-t-Bu and converted to the phosphonium salts with methyl iodide or ethyl bromide. These are the first reported π-complexes of phosphonium salts. The complex (π-C₅H₅Ni)₂Ph₂PC₂-t-Bu forms the novel mixed metal derivative [PdCl₂][(π-C₅H₅Ni)₂Ph₂PC₂-t-Bu]₂ from bis(benzonitrile)-palladium dichloride. The dicarbonyl complexes Ni(CO)₂(Ph₂PC₂R)₂ (R  t-Bu, Ph), the phosphine oxide complex (π-C₅H₅Ni)₂(Ph₂P(O)C₂Ph) and the trinuclear nickel carbonyl derivative Ni(CO)₃[(π-C₅H₅Ni)₂Ph₂PC₂Ph] are described.