Structure and Luminescence Studies of Salts of the Helical Dication, [Au2(µ-bis(diphenylphosphine)ethane)2]2+ and Comparison with Salts of [Au2(µ-bis(diphenylphosphine)propane)2]2.

Six salts ([Au2(µ-dppe)2](BF4)2·CHCl3, [Au2(µ-dppe)2](BF4)2·1,2-Cl2C2H4, [Au2(µ-dppe)2](PF6)2·CHCl3, [Au2(µ-dppe)2](PF6)2, [Au2(µ-dppe)2](SbF6)2, and [Au2(µ-dppe)2](OTf)2·2CHCl3), (dppe is bis(diphenylphosphine)ethane) containing the dication, [Au2(µ-dppe)2]2+, have been prepared and structurally characterized by single-crystal X-ray crystallography. Unlike the three-coordinate dppe-bridged dimers, Au2X2(µ-dppe)2 (X = Br, I), which show considerable variation in the distance between the gold(I) ions over the range 3.0995(10) to 3.8479(3) Å in various solvates, the structure of the helical dication, [Au2(µ-dppe)2], in the new salts is remarkably consistent with the Au···Au separation falling in the narrow range 2.8787(9) to 2.9593(5) Å. In the solid state, the six crystals display a green luminescence both at room temperature and at 77 K, which has been assigned as phosphorescence. However, solutions of the dication are not luminescent. Salts containing the analogous dication [Au2(µ-dppp)2](PF6)2 (dppp is bis(diphenylphosphine)propane) have been prepared to determine whether the longer bridging ligand might also twist into a helical shape. These salts include [Au2(µ-dppp)2](OTf)2 (OTf is triflate) and three crystalline forms of [Au2(µ-dppp)2](PF6)2: the solvate [Au2(µ-dppp)2](PF6)2·(CHCl3) and two polymorphs of the unsolvated salt. None of these crystals are luminescent, but all contain a similar dication, [Au2(µ-dppp)2]2+, that contains two nearly parallel, linear P-Au-P groups and a long separation between the gold ions that varies from 5.3409(4) to 5.6613(6)Å.

Self-Assembled Encapsulation of CuX2- (X = Br, Cl) in a Gold Phosphine Box-like Cavity with Metallophilic Au-Cu Interactions.

Synthetic routes to the crystallization of two new box-like complexes, [Au6(Triphos)4(CuBr2)](OTf)5·(CH2Cl2)3·(CH3OH)3·(H2O)4 (1) and [Au6(Triphos)4 (CuCl2)](PF6)5·(CH2Cl2)4 (2) (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine), have been developed. The two centrosymmetric cationic complexes have been structurally characterized through single-crystal X-ray diffraction and shown to contain a CuX2- (X = Br or Cl) unit suspended between two Au(I) centers without the involvement of bridging ligands. These colorless crystals display green luminescence (λem = 527 nm) for (1) and teal luminescence (λem = 464 nm) for (2). Computational results document the metallophilic interactions that are involved in positioning the Cu(I) center between the two Au(I) ions and in the luminescence.

Unsymmetrical Coordination of Bipyridine in Three-Coordinate Gold(I) Complexes.

The unsymmetrical coordination of gold(I) by 2,2'-bipyridine (bipy) in some planar, three-coordinate cations has been examined by crystallographic and computational studies. The salts [(Ph3P)Au(bipy)]XF6 (X = P, As, Sb) form an isomorphic series in which the differences in Au-N distances range from 0.241(2) to 0.146(2) Å. A second polymorph of [(Ph3P)Au(bipy)]AsF6 has also been found. Both polymorphs exhibit similar structures. The salts [(Et3P)Au(bipy)]XF6 (X = P, As, Sb) form a second isostructural series. In this series the unsymmetrical coordination of the bipy ligand is maintained, but the gold ions are disordered over two unequally populated positions that produce very similar overall structures for the cations. Although many planar, three-coordinate gold(I) complexes are strongly luminescent, the salts [(R3P)Au(bipy)]XF6 (R = Ph or Et; X = P, As, Sb) are not luminescent as solids or in solution. Computational studies revealed that a fully symmetrical structure for [(Et3P)Au(bipy)]+ is 7 kJ/mol higher in energy than the observed unsymmetrical structure and is best described as a transition state between the two limiting unsymmetrical geometries. The Au-N bonding has been examined by natural resonance theory (NRT) calculations using the "12 electron rule". The dominant Lewis structure is one with five lone pairs on Au and one bond to the P atom, which results in a saturated (12 electron) gold center and thereby inhibits the formation of any classical, 2 e- bonds between the gold and either of the bipy nitrogen atoms. The nitrogen atoms may instead donate a lone pair into an empty Au-P antibonding orbital, resulting in a three-center, four-electron (3c/4e) P-Au-N bond. The binuclear complex, [µ2-bipy(AuPPh3)2](PF6)2, has also been prepared and shown to have an aurophillic interaction between the two gold ions, which are separated by 3.0747(3) Å. Despite the aurophillic interaction, this binuclear complex is not luminescent.

The Preparation of Luminescent, Mechanochromic Molecular Containers from Non-Emissive Components: The Box Cations, [Au6 (Triphos)4 Br]5+ and [Au6 (Triphos)4 Br2 ]4.

Two new molecular boxes, the mono-bromo box [Au6 (Triphos)4 Br](SbF6 )5 ⋅6(CH2 Cl2 ), 4 mB, and the dibromo box, [Au6 (Triphos)4 Br2 ⋅H2 O](SbF6 )4 ⋅4(CH2 Cl2 ), 5 dB, have been prepared in crystalline form. Although constructed from non-luminescent components, both are strongly luminescent. Like its chloro counterpart, the mono-bromo box [Au6 (Triphos)4 Br](SbF6 )5 ⋅6(CH2 Cl2 ), 4 mB, is mechanochromic. Under grinding, it loses its luminescence. The bromo-bridged helicate, [(µ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ), 3µ-H, with a cation that is isomeric with the box [Au6 (Triphos)4 Br]5+ , has also been prepared and crystallographically characterized. Unlike its chloro analogue, [(µ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ) is not luminescent. Thus, the cation produced upon grinding may be the cation present in the bromo-bridged helicate, [(µ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ), 3µ-H. The dibromo box, [Au6 (Triphos)4 Br2 ⋅H2 O](SbF6 )4 ⋅4(CH2 Cl2 ), 5 dB, is not significantly mechanochromic.

Utilization of a Nonemissive Triphosphine Ligand to Construct a Luminescent Gold(I)-Box That Undergoes Mechanochromic Collapse into a Helical Complex.

Luminescent gold(I) complexes ([Au6(Triphos)4Cl](PF6)5·2(CH3C6H5), [Au6(Triphos)4Cl](AsF6)5·8(CH3C6H5), and [Au6(Triphos)4Cl](SbF6)5·7(CH3C6H5) where Triphos = bis(2-diphenylphosphinoethyl)phenylphosphine) with a boxlike architecture have been prepared and crystallographically characterized. A chloride ion resides at the center of the box with two of the six gold(I) ions nearby. Mechanical grinding of blue luminescent crystals containing the cation, [Au6(Triphos)4Cl]5+, results in their conversion into amorphous solids with green emission that contain the bridged helicate cation, [µ-Cl{Au3(Triphos)2}2]5+. A mechanism of the mechanochromic transformation is proposed. The structures of the blue-emitting helicate, [Au3(Triphos)2](CF3SO3)3·4(CH3C6H5)·H2O, and the green-emitting bridged-helicate, [µ-Cl{Au3(Triphos)2}2](PF6)5·3CH3OH have been determined by single crystal X-ray diffraction.

Formation of a Stable Complex, RuCl2(S2CPPh3)(PPh3)2, Containing an Unstable Zwitterion from the Reaction of RuCl2(PPh3)3 with Carbon Disulfide.

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. (31)P NMR studies indicate that the unsymmetrical dinuclear complex (SC)(Ph3P)2Ru(µ-Cl)3Ru(PPh3)2Cl is the initial product of the reaction of RuCl2(PPh3)3 with carbon disulfide. A path connecting the isolated products is presented.

Emissions savings in the corn-ethanol life cycle from feeding coproducts to livestock.

Environmental regulations on greenhouse gas (GHG) emissions from corn (Zea mays L.)-ethanol production require accurate assessment methods to determine emissions savings from coproducts that are fed to livestock. We investigated current use of coproducts in livestock diets and estimated the magnitude and variability in the GHG emissions credit for coproducts in the corn-ethanol life cycle. The coproduct GHG emissions credit varied by more than twofold, from 11.5 to 28.3 g CO(2)e per MJ of ethanol produced, depending on the fraction of coproducts used without drying, the proportion of coproduct used to feed beef cattle (Bos taurus) vs. dairy or swine (Sus scrofa), and the location of corn production. Regional variability in the GHG intensity of crop production and future livestock feeding trends will determine the magnitude of the coproduct GHG offset against GHG emissions elsewhere in the corn-ethanol life cycle. Expansion of annual U.S. corn-ethanol production to 57 billion liters by 2015, as mandated in current federal law, will require feeding of coproduct at inclusion levels near the biological limit to the entire U.S. feedlot cattle, dairy, and swine herds. Under this future scenario, the coproduct GHG offset will decrease by 8% from current levels due to expanded use by dairy and swine, which are less efficient in use of coproduct than beef feedlot cattle. Because the coproduct GHG credit represents 19 to 38% of total life cycle GHG emissions, accurate estimation of the coproduct credit is important for determining the net impact of corn-ethanol production on atmospheric warming and whether corn-ethanol producers meet state- and national-level GHG emissions regulations.

Residual effects of compost and plowing on phosphorus and sediment in runoff.

Manure application can lead to excessive soil test P levels in surface soil, which can contribute to increased P concentration in runoff. However, manure application often results in reduced runoff and sediment loss. Research was conducted to determine the residual effects of previously applied compost, plowing of soil with excessive soil test P, and application of additional compost after plowing on volume of runoff and loss of sediment and P in runoff. The research was conducted in 2004 and 2005 under natural rainfall events with plots of 11-m length where low-P and high-P compost had been applied during April 1998 to January 2001. During this initial application period, Bray-P1 in the surface 5-cm of depth was increased from 14 to 553 mg kg(-1) for the high-P compost. Inversion plowing in the spring of 2004 greatly decreased P levels in the surface soil and over the following year reduced runoff by 35% and total P losses by 51% compared with the unplowed compost treatments. Sediment loss was increased with plowing compared with the unplowed compost applied treatments but less than with the no-compost treatment. The application of additional compost after plowing increased surface soil P and dissolved reactive P (DRP) in runoff but did not increase particulate P in runoff. Unplowed compost-amended soil continued to reduce sediment loss but exhibited increased DRP loss even 5 yr after the last application. Plowing to invert excessively high-P surface soil was effective in reducing runoff and DRP loss.

Phosphorus runoff during four years following composted manure application.

Repeated manure application can lead to excessive soil test P (STP) levels and increased P concentration in runoff, but also to improved water infiltration and reduced runoff. Research was conducted to evaluate soil P tests in prediction of P concentration in runoff and to determine the residual effects of composted manure on runoff P loss and leaching of P. The research was conducted from 2001 to 2004 under natural runoff events with plots of 11-m length. Low-P and high-P compost had been applied during the previous 3 yr, resulting in total applications of 750 and 1150 kg P ha(-1). Bray-P1 in the surface 5 cm of soil was increased from 16 to 780 mg kg(-1) with application of high-P compost. Runoff and sediment losses were 69 and 120% greater with no compost than with residual compost treatments. Runoff P concentration increased as STP increased, but much P loss occurred with the no-compost treatment as well. Agronomic soil tests were predictive of mean runoff P concentration, but increases in STP resulted in relatively small increases in runoff P concentration. Downward movement of P was not detected below 0.3 m. In conclusion, agronomic soil tests are useful in predicting long-term runoff P concentration, and risk of P loss may be of concern even at moderate soil P levels. The residual effect of compost application in reducing sediment and runoff loss was evident more than 3 yr after application and should be considered in P indices.

Agroecosystems, nitrogen-use efficiency, and nitrogen management.

The global challenge of meeting increased food demand and protecting environmental quality will be won or lost in cropping systems that produce maize, rice, and wheat. Achieving synchrony between N supply and crop demand without excess or deficiency is the key to optimizing trade-offs amongst yield, profit, and environmental protection in both large-scale systems in developed countries and small-scale systems in developing countries. Setting the research agenda and developing effective policies to meet this challenge requires quantitative understanding of current levels of N-use efficiency and losses in these systems, the biophysical controls on these factors, and the economic returns from adoption of improved management practices. Although advances in basic biology, ecology, and biogeochemistry can provide answers, the magnitude of the scientific challenge should not be underestimated because it becomes increasingly difficult to control the fate of N in cropping systems that must sustain yield increases on the world's limited supply of productive farm land.