Plumbing systems of shallow level intrusive complexes

We have come a long way from simple straw and balloon models of magma plumbing systems to a more detailed picture of shallow level intrusive complexes. In this chapter, the sub-volcanic plumbing system is considered in terms of how we can define the types and styles of magma networks from the deep to the shallow subsurface. We look at the plumbing system from large igneous provinces, through rifted systems to polygenetic volcanoes, with a view to characterising some of the key conceptual models. There is a focus on how ancient magmatic centres can help us better understand magmatic plumbing. New innovative ways to consider and quantify magma plumbing are also highlighted including 3D seismic, and using the crystal cargo to help fingerprint key magma plumbing events. Conclusions are drawn to our understanding of the 3D plumbing system and how these recent advances can be helpful when exploring the other chapters of this contribution.

The syntheses, characterizations, X-ray crystal structures and properties of Cu(I) complexes of a bis-bidentate schiff base ligand

Bis-bidentate Schiff base ligand L and its two mononuclear complexes [CuL(CH3CN)(2)]ClO4 (1)and [CuL(PPh3)(2)]ClO4 (2)have been prepared and thoroughly characterized by elemental analyses, IR, UV-Vis, NMR spectroscopy and X-ray diffraction analysis. In both the complexes the metal ion auxiliaries adopt tetrahedral coordination environment. Their reactivity, electrochemical and photophysical behavior have been studied. Complex 1 shows reversible Cu-II/I couple with potential 0.74 V versus Ag/AgCl in CH2Cl2. At room temperature L is weakly fluorescent in CH2Cl2, however in Cu(I)complexes 1 and 2 the emission in quenched. (C) 2009 Elsevier B. V. All rights reserved.

N-H center dot center dot center dot O and C-H center dot center dotcenter dot O interaction mimicry in the 1:1 molecular complexes of 5,5-diethylbarbituric acid with urea and acetamide

The analogy between N-H center dot center dot center dot O and C-H center dot center dot center dot O intermolecular interactions is studied with variable temperature (180-100 K) single crystal X-ray diffraction analysis.5,5-Diethylbarbituric acid (barbital) forms isostructural molecular complexes (co-crystals) with urea (1) and acetamide (2) that respectively contain these analogous interactions.The behaviour of these two interactions as a function of temperature is very similar. This indicates that the C-H center dot center dot center dot O bond in barbital acetamide plays a similar chemical and structural role as does the N-H center dot center dot center dot O bond in barbital urea. The close relationship between these interactions and their comparable nature is further adduced from the formation of a ternary solid solution (3) of barbital, urea and acetamide. The fact that the C-H center dot center dot center dot O interaction in barbital acetamide is weaker than the N-H center dot center dot center dot O interaction in barbital urea is shown by the fact that acetamide is under expressed and urea is over expressed with respect to the quantities of these substances present in solution prior to crystallization of these ternary crystals.

Diphenyl sulphoxide complexes of some oxocations

Diphenyl sulphoxide (DPSO) complexes of TiO2+, ZrO2+, VO2+ and UO22+ have been prepared and characterized by physicochemical methods. The complexes have the formulae: [TiO(DPSO)5]2 (ClO4)4, [ZrO(DPSO)6] (ClO4)2, [VO(DPSO)5](ClO4)2, [VO(DPSO)3Cl2], [UO2-(DPSO)4] (ClO4)2, [UO2(DPSO)2Cl2],[UO2(DPSO)2(NO3)2]and[UO2(DPSO)2(CH3COO)2]. The i.r. spectra show the coordination through the oxygen of the sulphoxide in all the complexes. The spectroscopic, conductivity and crysoscopic studies indicate the ionic nature of the perchlorate, while the chloride, nitrate and acetate are coordinated, the last two being bidentate. The probable stereochemistry of the complexes is discussed. The complexes decompose exothermally.

Photocytotoxic Lanthanum(III) and Gadolinium(III) Complexes of Phenanthroline Bases Showing Light-Induced DNA Cleavage Activity

Lanthanide complexes of formulation [La(B)(2)(NO3)(3)] (1-3) and [Gd(B)(2)(NO3)(3)] (4-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 4),dipyrido[3,2-d2',3'-f]quinoxaline (dpq in 2,5) and dipyrido[3,2-a2',3'-c]phenazine (dppz in 3, 6), have been prepared, characterized from physicochemical data, and their photoinduced DNA and protein cleavage activity studied The photocytotoxicity of the dppz complexes 3 and 6 has been studied using HeLa cancer cells. The complexes exhibitligand centered bands in the UV region The dppz complexes show thelowest energy band at 380 nm in N,N-dimethylformamide (DMF) The La(III)complexes are diamagnetic. The Gd(III) complexes (4-6) have magneticmoments that correspond to seven unpaired electrons The complexes are1(.)1 electrolytic in aqueous DMF The dpq and dppz complexes in DMFshow ligand-based reductions. The complexes display moderate binding propensity to calf thymus DNA giving binding constant values in the range of 5.7 x 10(4)-5.8 x 10(5) M-1 with a relative order. 3, 6 (dppz)> 2, 5 (dpq) > 1, 4 (phen) The binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes do not show any hydrolytic cleavage of plasmid supercoiled pUC19 DNA. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form onexposure to UV-A light of 365 nm at nanomolar complex concentration. Mechanistic studies reveal the involvement of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) as the cleavage active species.The complexes show binding propensity to bovine serum albumin (BSA)protein giving K-BSA values of similar to 10(5) M-1. The dppz complexes 3 and 6 show BSA protein cleavage activity in UV-A light of 365 nm The dppz complexes 3 and 6 exhibit significant photocytotoxicity in HeLa cells giving respective IC50 values of 341 nM and 573 nM in UV-A light of 365 nm for an exposure time of 15 min (IC50 > 100 mu M in dark for both the complexes) Control experiments show significant dark and phototoxicity of the dppz base alone (IC50 = 413 nM in light with 4 h incubation in dark and 116 mu M in dark with 24 h incubation). A significant decrease in the dark toxicity of the dppz base is observedon binding to the lanthanide ions while retaining similar phototoxicity.

Dimethyl sulphoxide and dimethyl formamide complexes of Mn(III) perchlorate

Dimethyl sulphoxide (DMSO) and dimethyl formamide (DMF) complexes of Mn(III) perchlorate have been prepared and their conductivity, magnetic susceptibility and i.r. and electronic spectra studied. The complexes behave as uni-trivalent electrolytes in acetonitrile. Their magnetic moments of 5·1 B.M. show them to be of high spin type. Infra-red spectra show that oxygen is the donor atom in both complexes. The spin allowed electronic transition for d4 system, around 20,000 cm−1, ascribable to the 5Eg → 5T2g transition, suggests an octahedral configuration for these complexes

Ligand series from V = O stretching frequency of oxovanadium(IV) complexes*1

A ligand series obtained from V = O stretching frequencies for different monomeric complexes of oxovanadium(IV) is shown to parallel the nephelauxetic series. The ligand series obtained from streching frequencies of other systems are also shown to compare well with the nephelauxetic series rather than the spectrochemical series.

Diphenyl sulphoxide complexes of some divalent metal ions*1

Diphenyl sulphoxide (DPSO) complexes of some divalent metal perchlorates and chlorides are prepared The perchlorates of Mn, Co, Ni, Zn and Cd have the general formula [M(DPSO)6](CIO4)2. The Cu(II) complex is found to have the composition [Cu(DPSO)4] (CIO42. The chloro complex having the formula ZnCl2. 2DPSO, CdCl2.DPSO, HgCl2. DPSO and PdCl2. 2 DPSO have also been obtained. Infrared spectra indicate that the DPSO complexes of Mn, Co, Ni, Cu and Zn are oxygen-bonded while those of Cd, Hg and Pd are sulphur-bonded. The magnetic susceptibility and the optical spectral data reveal octahedral coordination for Mn, Co and Ni complexes. From the electronic spectra of Co and NI complexes, the ligand field parameters, Dq and β, are calculated.

Antipyrine complexes of rare-earth nitrates

Antipyrine complexes of eight rare-earth nitrates of the composition M(C11H12N2O)3 (NO3)3 where M = La, Ce, Pr, Nd, Sm, Gd, Er, and Y, have been prepared by a new, simple method and characterised. The complexes undergo exothermic decomposition at ~3oo°C. Infrared and U.V. spectral studies of the complexes indicate that antipyrine coordinates to metal through oxygen. The nature of the nitrate bonding is discussed in the light of infrared evidence, and conductivity studies in nitromethane and dimethylformamide.

Dimethyl sulphoxide complexes of lanthanide and yttrium nitrates

Dimethyl sulphoxide complexes of lanthanide and yttrium nitrates of the general formula M(DMSO)n(NO3)3 where M = La, Ce, Pr, Nd, Sm or Gd; n = 4 and M = Y, Ho or Yb; n = 3 have been isolated and characterized. The i.r. data besides excluding the presence of D3h nitrate, reveal co-ordination through the oxygen atom of the dimethyl sulphoxide. The complexes are monomeric in acetonitrile. Molecular conductance data in acetone, acetonitrile, dimethyl formamide and dimethyl sulphoxide suggest a co-ordination number of eight for the lighter lanthanides and seven for yttrium and the heavier lanthanides.

Antipyrine complexes of rare earth perchlorates

Rare earth perchlorate-antipyrine (ap) complexes of the formula Ln (ClO4)3.6 ap have been prepared and characterised. Infrared and electronic spectra showed the co-ordination through carbonyl oxygen. Conductivity and molecular weight data indicated a co-ordination number of six for these complexes.

Dimethyl sulphoxide complexes of rare-earth perchlorates

Dimethylsulphoxide (DMSO) complexes of rare-earth perchlorates of the formula M(ClO4)3·n DMSO (M = La, Ce, Pr and Nd, n = 8; M = Sm, Gd and Y, n = 7) have been prepared. I.r. studies indicate co-ordination through oxygen. Cryoscopic and conductivity data show co-ordination number of 7 and 8.

Oxalato complexes of oxovanadium (IV)

Oxalato oxovanadium (IV) complexes with neutral ligand molecules like dimethyl sulphoxide (DMSO) and antipyrine (Apy), VOOX·2DMSO and VOOX·2Apy and complex oxalates of oxovanadium (IV)-(NH4)2[VOOX2]·2H2O, (NH4)2[(VO)2OX3]·6H2O and (NH4)2[(VO)2OX3] have been prepared and characterized by different methods. In the divanadyl complexes, V-V and V-O-V-O types of bonding are shown to be absent by magnetic and spectral data and a bridged oxalato group co-ordinated to the two vanadium atoms is shown to be present, in addition to the usual bidentate oxalate groups. The possible stereochemical arrangements are indicated for the complexes.