Synthesis and coordination properties of new bis(phosphinomethyl)pyridine N,P,P'-trioxides.

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.

Synthesis and coordination chemistry of 2,6-bis(diphenylphosphinomethyl)phenol P,P'-dioxides.

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.

Basicity of uranyl oxo ligands upon coordination of alkoxides.

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.

Synthesis and molecular structure of a plutonium(IV) coordination complex: [Pu(NO3)2(2,6-[(C6H5)2P(O)CH2]2C5H3NO)2](NO3)2x1.5H2Ox0.5MeOH.

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.

Celestial Mechanics, Sea-Level Changes, and Intertidal Ecology.

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.

Effects of productivity, consumers, competitors, and El Niño events on food chain patterns in a rocky intertidal community.

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.

Wave energy and intertidal productivity.

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.

Disaster, Catastrophe, and Local Persistence of the Sea Palm Postelsia palmaeformis.

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.

Disturbance, patch formation, and community structure.

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.

Intertidal community structure : Experimental studies on the relationship between a dominant competitor and its principal predator.

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.

Species Introduction in a Tropical Lake: A newly introduced piscivore can produce population changes in a wide range of trophic levels.

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.