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The annual brown alga Postelsia palmaeformis is dependent for its survival on short-distance dispersal (SDD) where it is already established, as well as occasional long-distance colonization of novel sites. To quantify SDD, we transplanted Postelsia to sites lacking established plants within ≥10 m. The spatial distribution of the first naturally produced sporophyte generation was used to fit dispersal kernels in a hierarchical Bayesian framework. Mean dispersal distance within a year ranged from 0.16 to 0.50 m across sites; 95% of the recruits were within 0.38-1.32 m of the transplant. The fat-tailed exponential square root kernel was the best among the candidate models at describing offspring density and dispersal. Independent measurements of patch size over two to five generations permitted an evaluation of whether models parameterized by individual-level data could adequately predict longer-term persistence and spread at the patch scale. The observed spread rates generally fell within the 95% predictive intervals. Finally, Postelsia was eliminated from 14 occupied sites that were then followed for ≥27 yr. The probability of invasion when unoccupied declined and the probability of extinction when occupied increased with distance from the nearest propagule source. Sites >10 m from a source were rarely invaded, and one initially densely populated site isolated by 39 m has remained Postelsia-free since 1981. In spite of dispersal that is almost entirely within 2 m of the parent, the ability of our models to capture the observed dynamics of Postelsia indicates that short-range dispersal adequately explains the persistent and thriving Postelsia metapopulation on Tatoosh Island. However, the presence of Postelsia over a 2000-km coastal range with many gaps >1 km makes it clear that rare long-distance dispersal must be required to explain the geographic range of the species., (© 2017 by the Ecological Society of America.)

Coralline algae are conspicuous members of many marine assemblages, especially those characterized by intense grazing pressure. We explored whether articulated species, especially Corallina vancouveriensis, depend on grazing invertebrates to both establish and flourish in an exposed rocky intertidal setting, and whether this plant-grazer relationship varied over more than three orders of magnitude (≈100->300,000 μm). Three experimental manipulations, supplemented by observations on recruitment, demonstrated that (i) C. vancouveriensis failed to recover rapidly from disturbed areas when grazers were experimentally excluded; (ii) recruitment occurred in the presence of grazers; (iii) increasing surface texture of molded surfaces enhanced coralline recruitment more when grazers were present; and (iv) settlement occurred predominately in microtopographical low areas of a molded surface, whereas a competitively superior fleshy red alga tended to recruit to high areas. These results confirm that coralline algal establishment and persistence are enhanced by grazers and reveal that this relationship is consistent over a range of biologically relevant scales., (© 2016 Phycological Society of America.)

Ecologists have identified numerous keystone species, defined as organisms that have outsized ecological impacts relative to their biomass. Here we identify human beings as a higher-order or 'hyperkeystone' species that drives complex interaction chains by affecting other keystone actors across different habitats. Strong indirect effects and a global reach further characterize these interactions and amplify the impacts of human activities on diverse ecosystems, from oceans to forests. We require better understanding of hyperkeystone interaction chains most urgently, especially for marine species and terrestrial large carnivores, which experience relatively higher exploitation rates than other species. This requires innovative approaches that integrate the study of human behavior with food-web theory, and which might provide surprising new insights into the complex ecology of our own species., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Seawater pH and the availability of carbonate ions are decreasing due to anthropogenic carbon dioxide emissions, posing challenges for calcifying marine species. Marine mussels are of particular concern given their role as foundation species worldwide. Here, we document shell growth and calcification patterns in Mytilus californianus, the California mussel, over millennial and decadal scales. By comparing shell thickness across the largest modern shells, the largest mussels collected in the 1960s-1970s and shells from two Native American midden sites (∼1000-2420 years BP), we found that modern shells are thinner overall, thinner per age category and thinner per unit length. Thus, the largest individuals of this species are calcifying less now than in the past. Comparisons of shell thickness in smaller individuals over the past 10-40 years, however, do not show significant shell thinning. Given our sampling strategy, these results are unlikely to simply reflect within-site variability or preservation effects. Review of environmental and biotic drivers known to affect shell calcification suggests declining ocean pH as a likely explanation for the observed shell thinning. Further future decreases in shell thickness could have significant negative impacts on M. californianus survival and, in turn, negatively impact the species-rich complex that occupies mussel beds., (© 2016 The Author(s).)

Stepwise syntheses of 2-{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]C5H4NO (6), 2-{[2-(diphenylphosphoryl)acetamido]methyl}-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]-6-[Ph2P(O)CH2]C5H3NO (7) and 2,6-bis{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2,6-[Ph2P(O)CH2C(O)N(H)CH2]2C5H3NO (8), are reported along with spectroscopic characterization data and single crystal X-ray diffraction structure determination for 6·2H2O, 7 and 2,6-[Ph2P(O)CH2C(O)N(H)CH2]2C5H3N·MeOH 18·MeOH, the pyridine precursor of 8. Molecular mechanics computations indicate that 6, 7 and 8 should experience minimal steric hindrance to donor group reorganization that would permit tridentate, tetradentate and pentadentate docking structures for the respective ligands on lanthanide cations. However, crystal structure determination for the lanthanide complexes, {[Yb(6)(NO3)3]·(MeOH)}n, {[Lu(6)(NO3)3]·(MeOH)}n, [Er(6)2(H2O)2](NO3)3·(H2O)4}n, {[La(13)(NO3)3(MeOH)]·(MeOH)}n, {[Eu(7)(NO3)2(EtOAc)0.5(H2O)0.5](NO3)}2·MeOH and [Dy3(7)4(NO3)4(H2O)2](NO3)5·(MeOH)5·(H2O)2 reveal solid-state structures with mixed chelating/bridging ligand : Ln(III) interactions that employ lower than the maximal denticity. The binding of 6 and 7 with Eu(III) in the solid state and in MeOH solutions is also accessed by emission spectroscopy. The acid dependence for solvent extractions with 6 and 7 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions is described and compared with the behavior of n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (OPhDiBCMPO, 1b) and 2-[(diphenyl)phosphinoylmethyl]pyridine N-oxide (DPhNOPO, 4a).

Syntheses for new ligands based upon dibenzothiophene and dibenzothiophene sulfone platforms, decorated with phosphine oxide and methylphosphine oxide donor groups, are described. Coordination chemistry of 4,6-bis(diphenylphosphinoylmethyl)dibenzothiophene (8), 4,6-bis(diphenylphosphinoylmethyl)dibenzothiophene-5,5-dioxide (9) and 4,6-bis(diphenylphosphinoyl)dibenzothiophene-5,5-dioxide (10) with lanthanide nitrates, Ln(NO3)3·(H2O)n is outlined, and crystal structure determinations reveal a range of chelation interactions on Ln(III) ions. The nitric acid dependence of the solvent extraction performance of 9 and 10 in 1,2-dichloroethane for Eu(III) and Am(III) is described and compared against the extraction behavior of related dibenzofuran ligands (2, 3; R = Ph) and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (4) measured under identical conditions.

Syntheses for a set of new ligands containing one or two carbamoylmethylphosphine oxide (CMPO) fragments appended to pyridine and pyridine N-oxide platforms are described. Molecular mechanics analyses for gas phase lanthanide-ligand interactions for the pyridine N-oxides indicate that the trifunctional NOPOCO molecules, 2-{[Ph2P(O)][C(O)NEt2]C(H)}C5H4NO (7) and 2-{[Ph2P(O)][C(O)NEt2]CHCH2}C5H4NO (8), and pentafunctional NOPOP'O'COC'O' molecules, 2,6-{[Ph2P(O)][C(O)NEt2]C(H)}2C5H3NO (9) and 2,6-{[Ph2P(O)][C(O)NEt2]CHCH2}2C5H3NO (10), should be able to adopt, with minimal strain, tridentate and pentadentate chelate structures, respectively. As a test of these predictions, selected lanthanide coordination chemistry of the N-oxide derivatives was explored. Crystal structure analyses reveal the formation of a tridentate NOPOCO chelate structure for a 1:1 Pr(III) complex containing 7 while 8 adopts a mixed bidentate/bridging monodentate POCO/NO binding mode with Pr(III). Tridentate and tetradentate chelate structures are obtained for several 1:1 complexes of 9 while a pentadentate chelate structure is observed with 10. Emission spectroscopy for one complex, [Eu(9)(NO3)3], in methanol, shows that the Eu(III) ion resides in a low-symmetry site. Lifetime measurements for methanol and deuterated methanol solutions indicate the presence of four methanol molecules in the inner coordination sphere of the metal ion, in addition to the ligand, with the nitrate anions most likely dissociated. The solvent extraction performance of 7-10 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions was analyzed and compared with the performance of 2,6-bis(di-n-octylphosphinoylmethyl)pyridine N-oxide (TONOPOP'O') and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (OPhDiBCMPO) measured under identical conditions.

A four-step synthesis for 4,6-bis(diphenylphosphinoylmethyl)dibenzofuran (4) from dibenzofuran and a two-step synthesis for 4,6-bis(diphenylphosphinoyl)dibenzofuran (5) are reported along with coordination chemistry of 4 with In(III), La(III), Pr(III), Nd(III), Er(III), and Pu(IV) and of 5 with Er(III). Crystal structure determinations for the ligands, 4·CH(3)OH and 5, the 1:1 complexes [In(4)(NO(3))(3)], [Pr(4)(NO(3))(3)(CH(3)CN)]·0.5CH(3)CN, [Er(4)(NO(3))(3)(CH(3)CN)]·CH(3)CN, [Pu(4)Cl(4)]·THF and the 2:1 complex [Nd(4)(2)(NO(3))(2)](2)(NO(3))(2)·(H(2)O)·4(CH(3)OH) are described. In these complexes, ligand 4 coordinates in a bidentate POP'O' mode via the two phosphine oxide O-atoms. The dibenzofuran ring O-atom points toward the central metal cations, but in every case it is more than 4 Å from the metal. A similar bidentate POP'O' chelate structure is formed between 5 and Er(III) in the complex, {[Er(5)(2)(NO(3))(2)](NO(3))·4(CH(3)OH)}(0.5), although the nonbonded Er···O(furan) distance is reduced to ∼3.6 Å. The observed bidentate chelation modes for 4 and 5 are consistent with results from molecular mechanics computations. The solvent extraction performance of 4 and 5 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions is described and compared against the extraction behavior of n-octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (OΦDiBCMPO) measured under identical conditions.

Until recently, large apex consumers were ubiquitous across the globe and had been for millions of years. The loss of these animals may be humankind's most pervasive influence on nature. Although such losses are widely viewed as an ethical and aesthetic problem, recent research reveals extensive cascading effects of their disappearance in marine, terrestrial, and freshwater ecosystems worldwide. This empirical work supports long-standing theory about the role of top-down forcing in ecosystems but also highlights the unanticipated impacts of trophic cascades on processes as diverse as the dynamics of disease, wildfire, carbon sequestration, invasive species, and biogeochemical cycles. These findings emphasize the urgent need for interdisciplinary research to forecast the effects of trophic downgrading on process, function, and resilience in global ecosystems.

An efficient three step synthesis of (benzoxazol-2-ylmethyl)phosphonic acid (6-H(2)) is described along with IR, mass spectrometry (MS), and (1)H, (13)C, and (31)P NMR spectroscopic characterization data, and a single crystal X-ray diffraction structure determination. 6-H(2) is unstable in acidic aqueous solutions (pH < 4) undergoing ring-opening to give [(2-hydroxyphenylcarbamoyl)methyl] phosphonic acid (7-H(2)) that is characterized by IR, MS, and NMR methods. The protonation constants (pK(a)) for 7-H(2) have been measured, and crystal structure determinations for (NH(4))(7-H) and K(7-H)·DMF are described. Reactions of NaOH and KOH with 6-H(2) in MeOH/H(2)O solutions led to isolation and crystal structure determinations of the salts [Na(6-H)·H(2)O](2), K(6-H), Na(3)(6)(6-H)·H(2)O, and [K(2)(6)](2)·3H(2)O. The complexation reactions of 7-H(2) with La(III), Nd(III), and Gd(III), as a function of pH, were also examined by titrametric methods, and a model for the 1:1 anion binding with Ln(III) cations is proposed.

The reactions of (Me(3)Si)(3)Al, Me(3)Al, Et(3)Al, and i-Bu(3)Al with 1,3,4,5,6-pentamethyl-2-aminoborazine have been examined. An amine alane adduct (Me(3)Si)(3)Al.NH(2)B(3)(Me)(2)N(3)Me(3) (1) and several elimination products [(Me(3)Si)(2)AlN(H)B(3)(Me)(2)N(3)Me(3)](2) (2), [(Me(3)SiAl)(4)(Me(3)SiN)(3)NH] (3), [Me(2)AlN(H) B(3)(Me)(2)N(3)Me(3)](2) (4), [Et(2)AlN(H) B(3)(Me)(2)N(3)Me(3)](2) (5), and [i-Bu(2)AlN(H) B(3)(Me)(2)N(3)Me(3)](2) (6) have been isolated. Compounds 1, 2, 4-6 have been spectroscopically characterized, and single crystal X-ray diffraction structure determinations have been completed for 1-4 and 6. The molecular chemistry provides insight into the reaction of Me(3)Al and 1,3,5-N-trimethyl-2,4,6-B-triaminoborazine that, upon pyrolysis, produces AlN/BN composite ceramic materials.

A synthetic route for the formation of 2-[bis(2-trifluoromethylphenyl)phosphinoylmethyl]pyridine N-oxide (1c) and 2-[bis(3,5-trifluoromethylphenyl)phosphinoylmethyl]pyridine N-oxide (1d) was developed and the new ligands characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The coordination chemistry of 1c was examined with Yb(NO3)3 and the molecular structure of one complex, [Yb(1c)(NO3)3(DMF)].DMF.0.5H2O, was determined by single-crystal X-ray diffraction methods. The ligand is found to coordinate in a bidentate fashion, and this is compared against lanthanide coordination chemistry observed for the related ligand, [Ph2P(O)CH2] C5H4NO.

Ecological responses to climate change may occur gradually with changing conditions, or they may occur rapidly once some threshold or "tipping point" has been reached. Here, we use a high-resolution, 30-year data set on the upper vertical limit of a high intertidal alga to demonstrate that distributional shifts in this species do not keep pace with gradual trends in air temperature or sea level, but rather occur in sudden, discrete steps. These steps occur when unusually warm air temperatures are associated with unusually calm seas and are contingent in the sense that neither atmospheric nor sea conditions by themselves were sufficient to generate the underlying physiological challenge. Shifts in the upper limit did not correlate with large environmental perturbations such as El Niños; rather, they appeared to be associated with stochastic departures from otherwise gradual environmental trends. Our results exemplify the view that multiple environmental factors should be considered when attempting to understand ecological responses to climate change. Furthermore, punctuated responses such as those we have identified urge caution when attempting to infer causal mechanisms and project future distributional shifts using data of limited temporal resolution or scope.

Phosphinoyl Grignard-based substitutions on 2,6-bis(chloromethyl)pyridine followed by N-oxidation of the intermediate 2,6-bis(phosphinoyl)methylpyridine compounds with mCPBA give the target trifunctional ligands 2,6-bis[bis(2-trifluoromethylphenyl)phosphinoylmethyl]pyridine 1-oxide (2a) and 2,6-bis[bis(3,5-bis(trifluoromethyl)phenyl)phosphinoylmethyl]pyridine 1-oxide (2b) in high yields. The ligands have been spectroscopically characterized, the molecular structures confirmed by single crystal X-ray diffraction methods, and the coordination chemistry surveyed with lanthanide nitrates. Single crystal X-ray diffraction analyses are described for the coordination complexes Nd(2a)(NO(3))(3), Nd(2a)(NO(3))(3) x (CH(3)CN)(0.5), Eu(2a)(NO(3))(3), and Nd(2b)(NO(3))(3) x (H(2)O)(1.25); in each case the ligand binds in a tridentate mode to the Ln(III) cation. These structures are compared with the structures found for lanthanide coordination complexes of the parent NOPOPO ligand, [Ph(2)P(O)CH(2)](2)C(5)H(3)NO.

Synthetic routes to 2-(pyridin-2-yl)-N,N-diphenylacetamide and 2-(6-methylpyridin-2-yl)-N,N-diphenyl-acetamide are described along with results from the chemical oxidation of these compounds with peracetic acid, m-chloroperbenzoic acid, and OXONE. In each case, oxidations generate four products in varying amounts depending on the oxidant and reaction conditions. Each product has been characterized by spectroscopic methods and the molecular structures of several of the new compounds have been confirmed by X-ray crystallography.

The trifunctional ligands, [(HO)2P(O)CH2]2C6H2(R)OH, (5-H4)(R = CH3, Br) were prepared in good yield via an Arbusov reaction between P(OEt)3 and the respective 4-R-2,6-bis(chloromethyl)phenols followed by acidic aqueous hydrolysis and they were spectroscopically characterized by IR and NMR techniques. The ligand 5-H4-CH3 readily dissolves lanthanide hydroxide residues and it forms a crystalline complex from aqueous LaCl3 solutions. This complex was characterized by single crystal X-ray diffraction methods and found to adopt a complex 2-D lamellar network in the bc plane. The La(III) inner coordination sphere is seven coordinate formed by oxygen atoms from two water molecules and five phosphonate oxygen atoms from three different ligands. The phenolic oxygen atom is not involved in the ligand binding to La(III).

The compound 2,6-bis(N-tert-butylacetamide)pyridine (2) was obtained via a Ritter synthesis, and oxidation with oxone provided the title pyridine-N-oxide (3). The compounds were characterized by spectroscopic methods, and the molecular structure of the N-oxide was determined by single-crystal X-ray diffraction methods. The coordination chemistry with Eu(NO3)3 was examined by using 1:1 and 2:1 ligand/Eu ratios, and a single-crystal X-ray analysis for Eu(3)(NO3)3(H2O) was completed. The ligand 3 is found to chelate in a tridentate fashion on the Eu(III).

A multistep synthesis for 2-(2-pyridyl-N-oxide) ethylphosphonic acid 6-H2 is described along with its spectroscopic (IR, NMR) data and a single-crystal X-ray diffraction structure analysis. Combination of the ligand with Nd(OH)3 results in the formation of a complex Nd(6-H)3. Single-crystal X-ray diffraction analysis reveals a three-dimensional crystal network generated by hydrogen-bonded chains along the crystallographic c axis. The hydrogen bonds are formed between phosphonic acid anion (6-H)(-1) protons on one chain and pyridyl N-oxide oxygen atoms in neighboring chains. The asymmetric unit contains 1/3[Nd(6-H)3] and there are two unique Nd(III) atoms, each with point symmetry. As a result, each Nd(III) ion is bound to six (6-H)(-1) ligands and the symmetry about the Nd(III) ion is octahedral with each vertex occupied by a phosphonate oxygen atom. The Nd-O bond lengths are essentially identical: Nd(1)-O(3), 2.336 (1) A; Nd(2)-O(4), 2.340 (1) A. The monoanionic ligand (6-H)(-1), therefore, serves to bridge the unique Nd(III) centers.

Syntheses for 2-(pyridyl N-oxide) methylphosphonic acid, 1-H, and 2-(pyridyl N-oxide) hydroxymethylphosphonic acid, 4-H, are described, and the crystal structures of both ligands are presented. Combination of these ligands with freshly prepared erbium hydroxide results in the formation of the isostructural complexes Er(L(-))(3)(LH).8H(2)O. The crystal structure determinations of the complexes show that extensive hydrogen bonding links the individual eight coordinate Er(L(-))(3)(LH) molecular units into a 3-D structure.

New bifunctional and trifunctional organophosphorus ligands, 2-[(bis(2-ethylhexyl)phosphino)methyl]pyridine N,P-dioxide, DEH(MNOPO), and 2,6-bis[(bis(2-ethylhexyl)phosphino)methyl]pyridine N,P,P'-trioxide, TEH(NOPOPO), have been synthesized. In contrast with previously reported phenyl derivatives, the increased solubility of these ligands in normal paraffinic hydrocarbon solvents make them attractive reagents for actinide partitioning. While the bifunctional reagent DEH(MNOPO) interacts with Eu(3+) and Am(3+) comparatively weakly, the trifunctional TEH(NOPOPO) exhibits moderate to high ability to transfer the trisnitrato complexes of these ions into n-dodecane from acidic aqueous solutions. We report here the details of TEH(NOPOPO) and DEH(MNOPO) preparation and of their ability to extract HNO(3), Am(NO(3))(3), and Eu(NO(3))(3) into paraffinic hydrocarbons. The trifunctional TEH(NOPOPO) can extract up to two molecules of HNO(3). The dominant extracted species for both Am(NO(3))(3) and Eu(NO(3))(3) has two TEH(NOPOPO) ligands associated over the range of temperatures 10-40 degrees C. From the variation in the equilibrium coefficients for the phase transfer reactions as a function of temperature, we have calculated the enthalpies and entropies for extraction of HNO(3), Am(NO(3))(3), and Eu(NO(3))(3) into n-dodecane. Each metal nitrate is transferred into the organic phase in an exothermic process but opposed by an unfavorable (negative) entropy. The thermodynamic data are interpreted to indicate that the pyridine N-oxide is apparently a significantly weaker donor group for these metal ions than the phosphine oxides.

A series of uranyl aryloxide complexes has been prepared via metathesis reactions between [UO(2)Cl(2)(THF)(2)](2) and di-ortho-substituted phenoxides. Reaction of 4 equiv of KO-2,6-(t)()Bu(2)C(6)H(3) with [UO(2)Cl(2)(THF)(2)](2) in THF produces the dark red uranyl compound, UO(2)(O-2,6-(t)()Bu(2)C(6)H(3))(2)(THF)(2).THF, 1. Single-crystal X-ray diffraction analysis of 1 reveals a monomer in which the uranium is coordinated in a pseudooctahedral fashion by two apical oxo groups, two cis-aryloxides, and two THF ligands. A similar product is prepared by reaction of KO-2,6-Ph(2)C(6)H(3) with [UO(2)Cl(2)(THF)(2)](2) in THF. Single-crystal X-ray diffraction analysis of this compound reveals it to be the trans-monomer UO(2)(O-2,6-Ph(2)C(6)H(3))(2)(THF)(2), 2. Dimeric structures result from the reactions of [UO(2)Cl(2)(THF)(2)](2) with less sterically imposing aryloxide salts, KO-2,6-Cl(2)C(6)H(3) or KO-2,6-Me(2)C(6)H(3). Single-crystal X-ray diffraction analyses of [UO(2)(O-2,6-Cl(2)C(6)H(3))(2)(THF)(2)](2), 3, and [UO(2)Cl(O-2,6-Me(2)C(6)H(3))(THF)(2)](2), 4, reveal similar structures in which each U atom is coordinated by seven ligands in a pseudopentagonal bipyramidal fashion. Coordinated to each uranium are two apical oxo groups and five equatorial ligands (3, one terminal phenoxide, two bridging phenoxides, and two nonadjacent terminal THF ligands; 4, one terminal chloride, two bridging phenoxides, and two nonadjacent terminal THF ligands). Apparently, the phenoxide ligand steric features exert a greater influence on the solid-state structures than the electronic properties of the substituents. Emission spectroscopy has been utilized to investigate the molecularity and electronic structure of these compounds. For example, luminescence spectra taken at liquid nitrogen temperature allow for a determination of the dependence of the molecular aggregation of 3 on the molecular concentration. Electronic and vibrational spectroscopic measurements have been analyzed to examine trends in emission energies and stretching frequencies. However, comparison of the data for compounds 1-4 reveals that the innate electron-donating capacity of phenoxide ligands is only subtly manifest in either the electronic or vibrational energy distributions within these molecules.

In the low intertidal zone at Tatoosh Island, Washington, United States, minimal estimates of primary production can vary from 0 to an average of 86 kilograms of wet mass per square meter per year when the grazing assemblage is manipulated. Highly productive annual kelps (Laminariales) replace less productive perennial species when macroscopic grazers are reduced or absent, resulting in monodominant assemblages of Alaria marginata. Experiments were repeated in seven consecutive years. Increased species richness makes no significant additional contribution to annual production. Rather, a competitively superior species is favored when its enemies are reduced, suggesting that terrestrial perspectives on the role of biodiversity that are developed without considering consumers may not be general.

The 2,6-bis(diphenylphosphinomethyl)phenol-P,P'-dioxides, [Ph(2)P(O)CH(2)](2)C(6)H(2)(R)OH, with R = H (2a), Br (2b), Me (2c), (t)Bu (2d), were prepared via Arbusov reactions between Ph(2)POEt and the phenol derivatives (ClCH(2))(2)C(6)H(2)(R)OH. The compounds have been characterized by spectroscopic methods, and their coordination chemistry with lanthanide nitrates, Ln(NO(3))(3), has been surveyed. The 1:1 complexes [Er(2c)(NO(3))(3)].Me(2)CO and [Nd(2d)(NO(3))(3).Me(2)CO].Me(2)CO have been structurally characterized by single-crystal X-ray diffraction methods, and the ligands found to act as neutral tridentate chelates. No evidence was found for the formation of 2:1 L:M complexes suggesting that these derivatives of 2 are weaker chelators than the related 2,6-bis(diphenylphosphinomethyl)pyridine N,P,P'-trioxide chelates.

In a search for more hydrocarbon solvent soluble derivatives of the parent ligand, 2,6-[Ph(2)P(O)CH(2)](2)C(5)H(3)NO (1a), a series of new ligands, 2,6-[R(2)P(O)CH(2)](2)C(5)H(3)NO [R = Bz (1b); Tol (1c); Et (1d); Pr (1e); Bu (1f); Pn (1g); Hx (1h); Hp (1i); and Oct (1j)] and 2,6-[RR'P(O)CH(2)](2)C(5)H(3)NO [R = Ph, R' = Bz (2a); R = Ph, R' = Me (2b); R = Ph, R' = Hx (2c); R = Ph, R' = Oct (2d)], have been prepared by either Arbusov or Grignard substitutions on 2,6-bis(chloromethyl)pyridine followed by N-oxidation. The new ligands have been characterized by spectroscopic methods, and their coordination chemistry with selected lanthanide ions has been surveyed. Several 1:1 and 2:1 ligand/metal complexes have been isolated, and single-crystal X-ray diffraction analyses for Nd(2a)(NO(3))(3), Er(2a)(NO(3))(3), Yb(1d)(NO(3))(3), and [Nd(1c)(2)](NO(3))(3) are described. The new structural data are discussed in relation to the structures of complexes formed by 1a.

Uranium(VI) alkoxide complexes are prepared via metathesis reactions of [UO2Cl2(THF)2]2 with potassium alkoxides in nonaqueous media. The dark red compound U[OCH2C(CH3)3]6, 1, results from redistributive exchange of oxo and neopentoxide ligands between more than one uranium species. Single-crystal X-ray diffraction analysis of 1 reveals a monomer in which the uranium is coordinated in a pseudooctahedral fashion by six neopentoxide ligands. Imposition of steric congestion at the metal center prevents oxo-alkoxide ligand exchange in the reactions using more sterically demanding alkoxides. Simple metathesis between uranyl chloride and alkoxide ligands occurs in the synthesis of golden yellow-orange UO2(OCHPh2)2(THF)2, 2, and yellow UO2[OCH(tBu)Ph]2(THF)2, 3. Single-crystal X-ray diffraction analysis of 2 reveals a monomer in which the uranium is coordinated in a pseudooctahedral fashion by two apical oxo ligands, two diphenylmethoxide ligands occupying trans positions, and two tetrahydrofuran ligands. Coordination of diisopropylmethoxide allows for synthesis of a more complex binary alkoxide system. Single-crystal X-ray diffraction analysis of watermelon red [UO2(OCH(iPr)2)2]4, 4, reveals a tetramer in which each uranium is coordinated in a pseudooctahedral fashion by two apical oxo ligands, one terminal alkoxide, two bridging alkoxide ligands, and one bridging oxo ligand from a neighboring uranyl group. These compounds are characterized by elemental analysis, 1H NMR, infrared spectroscopy, and, for 1, 2, and 4, single-crystal X-ray diffraction analysis. Luminescence spectroscopy is employed to evaluate the extent of aggregation of compounds 2-4 in various solvents. Vibrational spectroscopic measurements of 2-4 imply that, in contrast to the case of uranyl complexes prepared in aqueous environments, coordination of relatively strongly donating alkoxide ligands allows for enhancement of electron density on the uranyl groups such that the uranyl U=O bonds are weakened. Crystal data are as follows. 1: monoclinic space group C2/m, a = 10.6192(8) A, b = 18.36(1) A, c = 10.6151(8) A, beta = 109.637(1) degrees, V = 1949.1(3) A3, Z = 2, dcalc = 1.297 g cm-3. Refinement of 2065 reflections gave R1 = 0.045. 2: monoclinic space group P2(1)/c, a = 6.1796(4) A, b = 15.669(1) A, c = 16.169(1) A, beta = 95.380(1) degrees, V = 1558.7(2) A3, Z = 2, dcalc = 1.664 g cm-3. Refinement of 3048 reflections gave R1 = 0.036. 4: tetragonal space group I4, a = 17.8570(6) A, b = 17.8570(6) A, c = 11.4489(6) A, V = 3650.7(3) A3, Z = 2, dcalc = 1.821 g cm-3. Refinement of 1981 reflections gave R1 = 0.020.

The trifunctional ligand 2,6-[(C6H5)2P(O)CH2]2 C5H3NO (1), in a mixed EtOH/MeOH solvent system, when combined with an aqueous nitric acid solution of Pu(IV), produces a 2:1 coordination complex, [Pu(1)2(NO3)2](NO3)2. A single crystal of [Pu(NO3)2(2,6-[(C6H5)2P(O)CH2]2C5H3NO)2](NO3)2x1.5H2Ox0.5MeOH was characterized by X-ray diffraction analysis. The crystal is monoclinic, space group P2(1)/n, with a = 19.1011(9) A, b = 18.2873(9) A, c = 21.507(1) A, alpha = gamma = 90 degrees, beta = 108.64(1) degrees, and Z = 4. Two neutral ligands (1) are bonded to the Pu(IV) ion in a tridentate fashion. Two nitrate ions also occupy inner sphere coordination positions, while two additional NO3- ions reside in the outer sphere. Comparison of the solution optical absorbance and solid diffuse reflectance spectra shows the same Pu(IV) chromophore exists in both solid and solution states.

The reactions of Me(2)SiCl(2), Ph(2)SiCl(2), and Ph(2)GeCl(2) with LiP(H)B(N(i)Pr(2))(2) in a 1:2 ratio and the reaction of Ph(2)SiCl(2) with LiP(H)B(N(i)Pr(2))[N(SiMe(3))(2)] in a 1:2 ratio give good yields of the respective diphosphinosilanes, Me(2)Si[P(H)B(N(i)Pr(2))(2)](2), Ph(2)Si[P(H)B(N(i)Pr(2))(2)](2), Ph(2)Ge[P(H)B(N(i)Pr(2))(2)](2), and Ph(2)Si[P(H)B(N(i)Pr(2))[N(SiMe(3))(2)]](2). These species, when combined with BuLi in a 1:2 ratio, give lithium diphosphinosilanes and -germanes of the general type (DME.Li)(2){[PB(NR(2))(2)](2)ER'(2)}. All of the species have been characterized by spectroscopic methods. The molecular structures of three of the lithio compounds, (DME.Li)(2){[PB(N(i)Pr(2))(2)](2)SiPh(2)} (11), (DME.Li)(2){[PB(N(i)Pr(2))N(SiMe(3))(2)](2)SiPh(2)} (15), and (DME.Li)(2){[PB(N(i)Pr(2))(2)](2)GePh(2)} (13), have been determined by X-ray diffraction techniques. 11 crystallized in the triclinic space group P&onemacr; with a = 11.071(2) Å, b = 14.937(3) Å, c = 18.080(4) Å, alpha = 91.31(3) degrees, beta = 101.23(3) degrees, gamma = 109.95(3) degrees, and Z = 2, and 13 crystallized in the triclinic space group P&onemacr; with a = 11.083(1) Å, b = 14.978(2) Å, c = 18.134(2) Å, alpha = 91.17(1) degrees, beta = 101.43(1) degrees, gamma = 110.05(1) degrees, and Z = 2. 15 crystallized in the monoclinic space group P2(1)/n with a = 11.939(2) Å, b = 24.516(3) Å, c = 21.572(3) Å, beta = 101.52(1) degrees, and Z = 4. The reactions of the lithio compounds were surveyed with R(2)ECl(2) reagents. The metathesis reactions are sluggish, but the 1:1 reaction of (DME.Li)(2){[PB(N(i)Pr(2))(2)](2)GePh(2)} with (t)Bu(2)SnCl(2) gave the four-membered-ring compound The 1:2 reaction of Me(2)(Cl)SiSi(Cl)Me(2) with LiP(H)B(N(i)Pr(2))(2) yielded the (borylphosphino)silane [Me(2)SiP(H)B(N(i)Pr(2))(2)](2).

The azidoborazines [Me(3)N(3)B(2)(Me)(2)B(N(3))] and [H(3)N(3)B(3)(N(3))(3)] were prepared from the combination of Me(3)SiN(3) and the chloroborazines [Me(3)N(3)B(2)(Me)(2)BCl] and (H(3)N(3)B(3)Cl(3)). The compounds have been characterized by analytical and spectroscopic methods. The molecular structure of [H(3)N(3)B(3)(N(3))(3)] has been confirmed by single-crystal X-ray diffraction techniques: triclinic space group P&onemacr; with a = 8.579(1) Å, b = 9.182(1) Å, c = 12.043(1) Å, alpha = 104.62(1) degrees, beta = 90.26(1) degrees, gamma = 110.74(1) degrees, and Z = 4. The thermal behavior of the azides have been examined by TGA/DTA. The explosion sensitivity of [H(3)N(3)B(3)(N(3))(3)], which contains 82.58% nitrogen by weight, has been accessed by drop weight impact, spark, and friction tests. These measurements indicate that [H(3)N(3)B(3)(N(3))(3)] is a relatively sensitive explosive. The Staudinger reactivity of the azides with Ph(3)P was examined, and [H(3)N(3)B(3)(N(3))(3)] was found to produce [Ph(3)P=NH(2)](N(3)). The molecular structure of this compound was determined by single-crystal X-ray diffraction techniques: orthorhombic space group P2(1)2(1)2(1) with a = 10.649(2) Å, b = 11.737(3) Å, c = 13.364(4) Å, alpha = beta = gamma = 90 degrees, Z = 4.

The 1:1 and 2:1 reactions of (Me(3)Si)(2)PLi.2THF with several amino chlorophosphanes have been surveyed. With (i)()Pr(2)NPCl(2), both reactant stoichiometries produce the four-membered ring compound (3) via different reaction schemes. Compound 3 combines with Fe(2)(CO)(9) to produce a monometallic complex (4) in which the Fe(CO)(4) fragment is bonded to one of the Me(3)SiP centers. With the cyclic hydrazino phosphane ClP(MeNNMe)(2)PCl only the bis-phosphane substitution product, (Me(3)Si)(2)PP(MeNNMe)(2)PP(SiMe(3))(2), is isolated. With the cyclic diazadiphosphetidine ((t)()BuNPCl)(2) a bis-phosphane substitution product [(t)()BuNPP(SiMe(3))(2)](2) (10) is formed along with a cage compound [((t)()BuNP)(2)P(SiMe(3))](2) (11). The new compounds have been characterized by spectroscopic techniques, and the molecular structure of 4 and 11 have been determined by X-ray crystallography.

Celestial mechanics has long been known to affect life on Earth, but exploration of these influences has been hampered by long temporal scales and complex biological relations. Here we report on a periodic fluctuation in tidal exposure driven by the 18.6-y oscillation of the moon's orbital inclination, which can change by almost 50% the average time that intertidal organisms are exposed to air. The temperature of nearshore water and the upper limits to mussels are shown to vary with the lunar oscillation. Such variation challenges the value of ecological and physiological generalizations based on snapshot measures, and highlights the value of long-term studies.

The 1:1 reactions with (R(3)P)(2)MCl(2) (M = Ni, Pd, and Pt) have been surveyed, and bicyclic cage compounds containing boron, phosphorus and transition metal (Ni, Pd, or Pt) atoms have been isolated and characterized. The molecular structures of the species (Et(3)P)(2)Pd(PBN(i)Pr(2))(2) (2), (Et(3)P)(2)Pd(PBtmp)(2) (3), and (Et(3)P)(2)Pt(PBN(i)Pr(2))(2) (4) have been determined by single-crystal X-ray diffraction techniques. 2 crystallized in the monoclinic space group C2/c with a = 20.212(4) Å, b = 10.225(1) Å, c = 17.460(2) Å, beta = 107.72(1) degrees, and Z = 4. 3 crystallized in the orthorhombic space group P2(1)2(1)2(1) with a = 12.606(1) Å, b = 12.618(1) Å, c = 24.221(3) Å, and Z = 4. 4 crystallized in the monoclinic space group C2/c with a = 20.195(3) Å, b = 10.187(2) Å, c = 17.280(2) Å, beta = 107.53(7) degrees, and Z = 4. The spectroscopic and structural features of the new cage compounds are discussed in relation to their main group element cage analogs.

The 1:1 reactions of [((i)()Pr(2)N)BP(H)B(N(i)()Pr(2))PLi.DME] (1) and [(tmp)BP(H)B(tmp)PLi.DME] (2; tmp = 2,2,6,6-tetramethylpiperidino) with organylhalostannanes have been examined, and stannyl-substituted diphosphadiboretanes, (R(2)N)BP(H)B(NR(2))PSn(Cl)R'(2) (R(2)N = (i)()Pr(2)N, tmp; R' = Me, (t)()Bu) have been isolated and characterized. Dehydrohalogenation of these compounds with (t)()BuLi produced bicyclic cage compounds P(2)(R(2)NB)(2)SnR'(2) (R(2)N = (i)()Pr(2)N (9), tmp (8); R' = (t)()Bu) or an oligomer [-P(R(2)NB)(2)PSn(R'(2))-] (R(2)N = tmp; R' = Me). The 2:1 reactions of R'(2)SnCl(2) with 1 and 2 have been studied, and with a small R' group (Me) a disubstitution product, [HP(tmpB)(2)P](2)SnMe(2) (11), is obtained. With a larger R' group ((t)()Bu), cage products P(2)(tmpB)(2)Sn(t)()Bu(2) and P(2)((i)()Pr(2)NB)(2)Sn(t)()Bu(2) are isolated. The molecular structures of 8 and 9 have been determined by single crystal X-ray diffraction techniques, and these structures and their spectroscopic features are discussed in relation to other boron-phosphorus cage compounds.

We experimentally manipulated nutrient input to a rocky intertidal community, using nutrient-diffusing flowerpots, to determine (i) whether nutrients limited intertidal productivity, (ii) how a large-scale oceanographic disturbance (an El Niño event) affected patterns of nutrient limitation, (iii) the relative impacts of molluscan grazers and nutrient limitation, and (iv) if responses to experimental nutrient addition among trophic levels were more consistent with prey-dependent or ratio-dependent food chain models. Nutrients measurably increased the abundance of micrograzers (amphipods and chironomid larvae), but not algal biomass, during the summer of an El Niño year. Nutrients had no effects in two non-El Niño years and during the autumn of an El Niño year. Adding nutrients did not affect food chain stability as assessed by temporal variation in algal biomass and micrograzer abundance. Large molluscan grazers caused large reductions in micrograzers and smaller reductions in algae, indicating consistent consumer effects. The results demonstrate that in this intertidal community, nutrient limitation can occur under conditions of nutrient stress, that top-down grazing effects are typically stronger than bottom-up nutrient effects, and that prey-dependent models are more appropriate than ratio-dependent models.

Two components of natural disturbance, its local intensity and frequency beyond a threshold level, limit a marine benthic alga to wave-swept shores. Transplant experiments indicate that the limited distribution is not due to physiological restriction. Instead, it requires predictable annual disturbance of moderate intensity for local persistence.

In the northeastern Pacific, intertidal zones of the most wave-beaten shores receive more energy from breaking waves than from the sun. Despite severe mortality from winter storms, communities at some wave-beaten sites produce an extraordinary quantity of dry matter per unit area of shore per year. At wave-beaten sites of Tatoosh Island, WA, sea palms, Postelsia palmaeformis, can produce > 10 kg of dry matter, or 1.5 x 10(8) J, per m(2) in a good year. Extraordinarily productive organisms such as Postelsia are restricted to wave-beaten sites. Intertidal organisms cannot transform wave energy into chemical energy, as photosynthetic plants transform solar energy, nor can intertidal organisms "harness" wave energy. Nonetheless, wave energy enhances the productivity of intertidal organisms. On exposed shores, waves increase the capacity of resident algae to acquire nutrients and use sunlight, augment the competitive ability of productive organisms, and protect intertidal residents by knocking away their enemies or preventing them from feeding.

Along exposed rocky intertidal shorelines of western North America the mussel Mytilus californianus exists as a characteristic, well-defined band. Measurements at Mukkaw Bay and Tatoosh Island, Washington State, suggest that the upper limit to distribution is constant. The lower limit is also predictably constant, as judged by photographs of the same areas taken up to 9 years apart. The band of mussels is formed by larval recruitment to a variety of substrates, especially the filamentous red alga Endocladia muricata. From the settlement site, if the mussels survive a series of predators including the starfish Pisaster ochraceus and a variety of carnivorous gastropods (Thais spp.), the mussles may be washed inward or migrate (be pushed) downward.When Pisaster was removed manually, the zonation pattern changed rapidly. Mussels advanced downward at Mukkaw Bay a vertical distance of 0.85 m in 5 years. No movement was observed on 2 adjacent control sites. At Tatoosh Island a maximum displacement of 1.93 m has been observed in 3 years; the slope there is 40°. Again, there was no change at control sites with Pisaster. At Mukkaw Bay over 25 species of invertebrates and benthic algae are excluded from occupancy of the primary substratum by mussels. The ecological dominance of mussels is discussed; predation is shown to enhance coexistence among potential competitors. A survival curve for Pollicipes polymerus indicates that the time course for interspecific competitive exclusion may be long (76 months). The clarity of the biological interrelationships and the constancy of pattern through time provide no support for the contention that intertidal communities are physically-controlled.

A model is developed to relate community structure to level of environmental disturbance in systems in which the effects of disturbance are localized in space and time. In general these disturbances create a pattern of spatio-temporal heterogeneity by renewing a limiting resource, thereby permitting utilization by species that are not dominant competitors. The proposed model predicts the frequency distribution of these renewed areas, with regard to size and age (colonization stage). The model thus allows one to relate overall system pattern to the local biology within these areas, to compare various areas with different levels of disturbance, and to predict the effects of new disturbance.

Probably in early 1967, a piscivore from South America, Cichla ocellaris, was introduced to Gatun Lake in the Panama Canal Zone. As this predator population spread through the lake, the initial effect was dramatic reductions in almost all secondary consumers. These species reductions produced, in turn, second- and third-order changes at other trophic levels of the ecosystem. The resulting changes in the lake community can be seen best by examining the general Gatun Lake food web. The decrease in numbers of the important planktivore Melaniris has resulted in changes within the zooplankton community, as illustrated by the cladoceran Ceriodaphnia. The tertiary-consumer populations, such as tarpon, black terns, kingfishers, and herons, formerly dependent on small fishes for food, appear less frequently in the Cichla areas of the lake. There has also been, possibly, a resurgence of the local mosquito populations (which are malaria vectors), caused by the reduction in the populations of insect-eating fishes. Even the primary producers may be affected by this introduction. Although at present the Gatun Lake ecosystem is undergoing rapid changes, we anticipate an eventual return to some form of equilibrium. However, it will be some time before we can evaluate the permanence or transience of the many changes produced in the trophic levels by the introduction of a single, top-level predator to this lake system.