Lewis Acid/Base Interaction Matrix Database


Type 23 Lewis Acid/Base Complexation Chemistry
Classical Inorganic Coordination Chemistry

              Ag+     +     Cl             AgCl
              Ni       +     4CO           Ni(CO)4
              Fe3+    +     6H2O         [Fe(H2O)6]3+
              Cu2+    +     4Cl          [CuCl4]2–

Bonding:

The nature of bonding in heavy metal complexes, particularly transition metal complexes, is a vast subject with a long history and is of great technological importance: indeed the term ‘complex’ was first used to describe coordinated transition metal ions.

The two most important bonding models are the electrostatic ligand-field theory and molecular orbital (MO) theory.

Ligand-field theory assumes that the metal cation + anionic ligand interaction is primarily ionic. However, the more demanding MO model is computationally more accessible.

The geometry of heavy metal complexes can usually be predicted by the valence shell electron pair repulsion VSEPR method, however, the effect of d and f orbitals must also be considered: [FeCl4] is tetrahedral but the d8 complex [PdCl4] is square planar.

Transition metal complex ions may exhibit Jahn-Tellar distortion: Wikipedia, Robert J. Lancashire page & ScienceWorld.

Charge: Complexes may be negatively charged, positively charged or they may be neutral.
Chemistry:

Lobe-HOMO Lewis bases form a multitude of complexes with heavy metal cations, indeed a great deal of classical inorganic coordination chemistry involves Type 23 complexation. Complexes may be linear, [AgCl2], tetrahedral, Ni(CO)4 or octahedral:

Heavy metals show multiple oxidation states due to loss of different numbers of d and f orbital electrons. Redox considerations can be as important as HOMO/LUMO interactions when predicting reactivity.

Heavy metal complexes are usually coloured due to electronic transitions involving d or f orbitals and spectroscopic study can be used to probe the nature of the bonding in the complex. Sometimes small changes in ligands give rise to large spectral changes, and sometimes not.

As a rule, d-d electronic transitions give rise to pale colors whereas charge-transfer transitions result in complexes with dark colours.

Transition metals are employed in many biological systems where a protein molecule has a heavy metal ion at the active site, including: Hemoglobin, zinc finger protein & cytochrome:

   

Structure of heme b                                                      Cytochrome c with heme c.

Industrial process catalysts may be heterogeneous (solid catalyst, liquid or gaseous reaction mixture) or homogeneous with respect to the reaction mixture. Wilkinson's catalyst, chlorotris(triphenylphosphine)rhodium(I), facilitates the homogeneous hydrogenation of alkenes:

The phosphine ligands can be modified so as to give a chiral versions of Wilkinson's catalyst that are able to catalyse asymmetric hydrogenation. This approach has been developed into the Monsanto method for the production of L-DOPA, from Wikipedia:

Note that the hydrogenation catalyst is in this reaction: [Rh(R,R')-DiPAMP, COD]+ [BF4], has a non-nucleophilic tetrafluoroborate (complex anion Lewis base) counter ion.

Congeneric Series: There are many congeneric series formed by ligand replacement.
Type 23 Lewis acid/base complex (generic)
Bismuth nitrate

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Bismuth sulfide

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Cadmium bromide

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Cadmium chloride

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Cadmium fluoride

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Cadmium iodide

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Cadmium oxide

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Cadmium sulfide

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Cerium(III) bromide

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Cerium(III) chloride

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Cerium(III) fluoride

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Cerium(III) iodide

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Cerium(III) oxide

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Cerium(IV) fluoride

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Cerium(IV) oxide

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Chelate (AS/A2 generic)

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Chlorohydrobis(triethylphosphine) platinium(II)

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Chromium carbonyl

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Chromium(II) bromide

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Chromium(II) chloride

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Chromium(II) fluoride

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Chromium(II) iodide

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Chromium(II) oxide

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Chromium(III) bromide

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Chromium(III) chloride

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Chromium(III) fluoride

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Chromium(III) hydroxide

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Chromium(III) iodide

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Chromium(III) oxide

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Chromium(IV) bromide

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Chromium(IV) chloride

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Chromium(IV) fluoride

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Chromium(IV) iodide

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Chromium(IV) oxide

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Chromium(V) fluoride

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Chromium(VI) fluoride

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Chromium(VI) oxide

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Cobalt(II) bromide

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Cobalt(II) carbonate

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Cobalt(II) chloride

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Cobalt(II) EDTA complex ion

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Cobalt(II) fluoride

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Cobalt(II) hydroxide

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Cobalt(II) iodide

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Cobalt(II) oxide

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Cobalt(II) sulfate

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Cobalt(II) sulfide

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Cobalt(II) tris(ethanedioate) complex ion

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Cobalt(II) tris(ethylenediamine) ion

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Cobalt(II,III) oxide

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Cobalt(III) chloride

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Cobalt(III) dichloro bis(ethylenediamine) complex ion

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Cobalt(III) fluoride

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Cobalt(III) hydroxide

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Cobalt(III) oxide

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Cobalt(IV) oxide

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Copper carbonate hydroxide

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Copper(I) bromide

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Copper(I) chloride

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Copper(I) cyanide

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Copper(I) fluoride

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Copper(I) iodide

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Copper(I) oxide

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Copper(I) sulfide

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Copper(I) thiocyanate

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Copper(II) bromide

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Copper(II) carbonate

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Copper(II) carbonate, basic

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Copper(II) chloride

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Copper(II) EDTA complex ion

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Copper(II) fluoride

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Copper(II) hydroxide

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Copper(II) nitrate

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Copper(II) oxide

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Copper(II) sulfate.5H2O

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Copper(II) sulfate

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Copper(II) sulfide

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Diamminosilver(I) ion

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Dichlorosilver(I) ion

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Dichlorotetraaquachromium(III) ion

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Dichlorotetraaquavanadium(III) ion

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Dicobalt octacarbonyl

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Dicyanosilver(I) ion

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Diiron nonacarbonyl

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Dimanganese decacarbonyl

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Dioxovanadium(V) ion

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Dithiosulfatosilver(I) ion

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Dysprosium bromide

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Dysprosium fluoride

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Dysprosium iodide

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Dysprosium oxide

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Dysprosium(III) chloride

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Erbium chloride hexahydrate

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Erbium fluoride

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Erbium iodide

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Erbium(III) bromide

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Erbium(III) oxide

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Europium(II) bormide

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Europium(II) chloride

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Europium(II) fluoride

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Europium(II) iodide

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Europium(III) bromide

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Europium(III) chloride

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Europium(III) fluoride

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Europium(III) iodide

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Europium(III) oxide

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Gadolinium bromide

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Gadolinium chloride

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Gadolinium fluoride

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Gadolinium iodide

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Gadolinium(III) oxide

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Gold(I) bromide

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Gold(I) chloride

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Gold(I) iodide

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Gold(I) oxide

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Gold(III) bromide

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Gold(III) chloride

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Gold(III) fluoride

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Gold(III) iodide

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Gold(III) oxide

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Haem

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Hafnium(III) bromide

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Hafnium(III) chloride

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Hafnium(III) iodide

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Hafnium(IV) bromide

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Hafnium(IV) chloride

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Hafnium(IV) fluoride

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Hafnium(IV) iodide

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Hafnium(IV) oxide

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Hexaamminochromium(III) ion

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Hexaamminocobalt(II) ion

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Hexaamminocobalt(III) ion

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Hexaaquaaluminium complex ion

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Hexaaquachromium(II) ion

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Hexaaquachromium(III) ion

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Hexaaquacobolt(II) ion

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Hexaaquacopper(II) ion

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Hexaaquairon(II) ion

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Hexaaquairon(III) ion

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Hexaaquamanganese(II) ion

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Hexaaquavanadium(II) ion

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Hexaaquavanadium(III) ion

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Hexafluoropalladium(IV)

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Hexahydroxychromium(III) ion

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Holmium bromide

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Holmium chloride

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Holmium fluoride

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Holmium iodide

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Holmium(III) oxide

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Iridium(III) bromide

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Iridium(III) chloride

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Iridium(III) fluoride

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Iridium(III) iodide

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Iridium(IV) bromide

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Iridium(IV) chloride

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Iridium(IV) fluoride

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Iridium(IV) iodide

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Iridium(IV) oxide

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Iridium(VI) fluoride

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Iron pentacarbonyl

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Iron(II) bipyridyl ion

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Iron(II) bromide

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Iron(II) carbonate

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Iron(II) chloride

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Iron(II) fluoride

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Iron(II) hydroxide

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Iron(II) iodide

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Iron(II) oxalate

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Iron(II) oxide

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Iron(II) sulfide

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Iron(II) tungstate

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Iron(II,III) oxide

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Iron(III) bromide

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Iron(III) chloride

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Iron(III) chlorosulfate

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Iron(III) fluoride

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Iron(III) hydroxide

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Iron(III) oxide

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Iron(III) sulfate pentahydrate

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Iron(III) tris(ethanedioate) complex ion

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Lanthanum bromide

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Lanthanum fluoride

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Lanthanum iodide

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Lanthanum(III) chloride

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Lanthanum(III) oxide

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Lead tetroxide

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Lead(II) acetate

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Lead(II) azide

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Lead(II) bromide

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Lead(II) carbonate

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Lead(II) chloride

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Lead(II) chromate

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Lead(II) fluoride

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Lead(II) iodide

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Lead(II) nitrate

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Lead(II) oxide

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Lead(II) permanganate

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Lead(II) phosphate

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Lead(II) sulfate

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Lead(II) sulfide

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Lead(IV) oxide

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Lead(IV) tetraacetate

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Lithium diorganocopper reagent (generic)

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Lutetium bromide

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Lutetium chloride

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Lutetium fluoride

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Lutetium iodide

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Lutetium oxide

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Magnesium hexahydroiron(II) complex

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Magnesium nickel hydride

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Magnesium pentahydrocobalt(I) complex

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Manganese dioxide

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Manganese sulfide

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Manganese(II) carbonate

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Manganese(II) hydroxide

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Manganese(II) tungstate

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Manganese (II, III) oxide

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Mercury(I) bromide

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Mercury(I) chloride

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Mercury(I) fluoride

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Mercury(I) iodide

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Mercury(I) oxide

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Mercury(I) sulfide

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Mercury(II) acetate

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Mercury(II) bromide

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Mercury(II) chloride

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Mercury(II) fluoride

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Mercury(II) fulminate

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Mercury(II) iodide

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Mercury(II) nitrate

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Mercury(II) oxide

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Mercury(II) sulfate

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Mercury(II) sulfide

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Molybdenum(II) bromide

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Molybdenum(II) chloride

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Molybdenum(II) iodide

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Molybdenum(III) bromide

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Molybdenum(III) chloride

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Molybdenum(III) fluoride

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Molybdenum(III) iodide

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Molybdenum(IV) bromide

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Molybdenum(IV) chloride

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MolybdenumIV) fluoride

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Molybdenum(IV) oxide

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Molybdenum(IV) sulfide

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Molybdenum(V) chloride

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Molybdenum(V) fluoride

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Molybdenum(V) oxide

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Molybdenum(VI) fluoride

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Molybdenum(VI) oxide

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Nickel carbonyl

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Nickel(II) bromide

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Nickel(II) carbonate

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Nickel(II) chloride

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Nickel(II) fluoride

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Nickel(II) hydroxide

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Nickel(II) iodide

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Nickel(II) oxide

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Nickel(II) sulfide

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Nickel(II) tris(ethylenediamine) ion

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Nickel(III) arsinide

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Niobium(II) oxide

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Niobium(III) bromide

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Niobium(III) chloride

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Niobium(III) iodide

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Niobium(III) oxide

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Niobium(IV) oxide

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Niobium(V) bromide

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Niobium(V) chloride

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Niobium(V) fluoride

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Niobium(V) iodide

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Niobium(V) oxide

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Octacarbonyldicobalt(0)

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pi-Organometallic (generic)

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Osmium(III) chloride

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Osmium(IV) bromide

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Osmium(IV) chloride

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Osmium(IV) fluoride

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Osmium(IV) iodide

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Osmium(IV) oxide

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Osmium(V) chloride

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Osmium(V) fluoride

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Osmium(VI) fluoride

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Osmium(VIII) fluoride

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Osmium(VIII) oxide

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Palladium(II) bromide

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Palladium(II) chloride

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Palladium(II) fluoride

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Palladium(II) iodide

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Palladium(II) oxide

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Palladium(IV) fluoride

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Pentaaquahydroxychromium(III) ion

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Pentaaquahydroxyiron(III) ion

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Pentaaquathiocyanatoiron(III) ion

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Pentaaquaoxovanadium(IV) ion

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Platinum(IV) hexafluoride

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Platinum(II) bromide

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Platinum(II) chloride

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Platinum(II) fluoride

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Platinum(II) iodide

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Platinum(II) oxide

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Platinum(II) tetrachloride ion

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Platinum(II,IV) oxide

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Platinum(III) chloride

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Platinum(III) iodide

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Platinum(IV) bromide

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Platinum(IV) chloride

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Platinum(IV) fluoride

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Platinum(IV) hexachloride ion

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Platinum(IV) iodide

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Platinum(IV) oxide

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Platinum(V) fluoride

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Platinum(VI) oxide

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Potassium permanganate

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Potassium tetrahydrozinc(II) complex

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Praseodymium(III) bromide

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Praseodymium(III) chloride

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Praseodymium(III) iodide

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Praseodymium(III) oxide

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Praseodymium(IV) oxide

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Rhenium(III) bromide

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Rhenium(III) chloride

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Rhenium(III) iodide

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Rhenium(IV) bromide

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Rhenium(IV) chloride

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Rhenium(IV) fluoride

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Rhenium(IV) iodide

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Rhenium(IV) oxide

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Rhenium(V) bromide

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Rhenium(V) chloride

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Rhenium(V) fluoride

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Rhenium(VI) fluoride

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Rhenium(VI) oxide

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Rhenium(VII) fluoride

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Rhenium(VII) oxide

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Ruthenium(III) bromide

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Ruthenium(III) chloride

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Ruthenium(III) fluoride

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Ruthenium(III) iodide

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Ruthenium(IV) chloride

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Ruthenium(IV) fluoride

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Ruthenium(IV) oxide

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Ruthenium(V) fluoride

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Ruthenium(VI) fluoride

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Ruthenium(VIII) oxide

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Samarium(II) bromide

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Samarium(II) chloride

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Samarium(II) fluoride

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Samarium(II) iodide

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Samarium(III) bromide

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Samarium(III) chloride

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Samarium(III) fluoride

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Samarium(III) iodide

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Samarium(III) oxide

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Scandium(II) carbide

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Scandium(III) bromide

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Scandium(III) chloride

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Scandium(III) fluoride

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Scandium(III) hexafluoride ion

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Scandium(III) iodide

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Scandium(III) oxide

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Silver bromate

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Silver bromide

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Silver carbonate

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Silver chloride

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Silver chromate(VI)

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Silver cyanide

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Silver difluoride

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Silver iodate

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Silver iodide

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Silver nitrate

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Silver oxalate

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Silver oxide

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Silver peroxide

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Silver phosphate

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Silver subfluoride

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Silver sulfate

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Silver sulfide

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Silver thiocyanate

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Silver(I) fluoride

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Tantalum(III) bromide

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Tantalum(III) chloride

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Tantalum(IV) bromide

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Tantalum(IV) chloride

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Tantalum(IV) iodide

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Tantalum(IV) oxide

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Tantalum(V) bromide

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Tantalum(V) chloride

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Tantalum(V) fluoride

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Tantalum(V) iodide

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Tantalum(V) oxide

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Technetium(IV) chloride

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Technetium(IV) oxide

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Technetium(V) fluoride

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Technetium(VI) fluoride

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Technetium(VI) oxide

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Technetium(VII) oxide

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Terbium bromide

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Terbium chloride

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Terbium fluoride

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Terbium iodide

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Terbium oxide

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Tetraamminodiaquacopper(II) ion

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Tetraaquadihydroxycobalt(II)

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Tetraaquadihydroxycopper(II)

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Tetraaquadihydroxyiron(II)

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Tetracarbonylethylcobalt(I)

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Tetracarbonylhydrocobalt(I)

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Tetrachlorocobolt(II) ion

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Tetrachlorocopper(II) ion

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Tetrachlorogold(III)

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Tetra-ethyl lead

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Tetrahydroxyaluminate ion

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Tetrakis(triphenyl phosphine)palladium[0]

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Thallium(I) chloride

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Thallium(I) iodide

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Thallium(I) sulfide

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Thorium bromide

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Thorium chloride

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Thorium dioxide

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Thorium fluoride

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Thorium iodide

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Thulium bromide

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Thulium chloride heptahydrate

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Thulium fluoride

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Thulium iodide

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Thulium(III) oxide

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Tin(II) chloride

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Tin(II) oxide

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Tin(IV) oxide

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Titanium dioxide

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Titanium tetrachloride

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Titanium(II) bromide

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Titanium(II) chloride

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Titanium(II) iodide

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Titanium(II) oxide

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Titanium(III) bromide

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Titanium(III) chloride

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Titanium(III) fluoride

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Titanium(III) iodide

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Titanium(III) oxide

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Titanium(IV) bromide

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Titanium(IV) fluoride

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Titanium(IV) iodide

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Triaquatrihydroxyaluminium

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Triaquatrihydroxychromium(III)

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Triaquatrihydroxyiron(III)

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Tricarbonylhydrocobalt(I)

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Tricarbonylpropanoylcobalt(I)

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Tungsten(II) bromide

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Tungsten(II) chloride

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Tungsten(II) iodide

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Tungsten(III) bromide

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Tungsten(III) chloride

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Tungsten(III) iodide

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Tungsten(IV) bromide

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Tungsten(IV) chloride

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Tungsten(IV) fluoride

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Tungsten(IV) iodide

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Tungsten(IV) oxide

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Tungsten(V) bromide

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Tungsten(V) chloride

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Tungsten(V) fluoride

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Tungsten(VI) bromide

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Tungsten(VI) chloride

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Tungsten(VI) fluoride

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Tungsten(VI) oxide

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Tungsten(VI) oxide mono hydrate

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Uranium(III) bromide

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Uranium(III) chloride

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Uranium(III) fluoride

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Uranium(IV) bromide

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Uranium(IV) chloride

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Uranium(IV) fluoride

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Uranium(IV) iodide

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Uranium(IV) oxide

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Uranium(IV, VI) oxide

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Uranium(V) chloride

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Uranium(VI) fluoride

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Uranium(VI) oxide

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Vanadium carbonyl

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Vanadium(II) bromide

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Vanadium(II) chloride

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Vanadium(II) fluoride

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Vanadium(II) iodide

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Vanadium(II) oxide

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Vanadium(III) bromide

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Vanadium(III) chloride

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Vanadium(III) fluoride

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Vanadium(III) iodide

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Vanadium(III) oxide

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Vanadium(IV) bromide

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Vanadium(IV) chloride

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Vanadium(IV) fluoride

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Vanadium(IV) oxide

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Vanadium(V) fluoride

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Vanadium(V) oxide

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Ytterbium(II) bromide

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Ytterbium(II) chloride

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Ytterbium(II) fluoride

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Ytterbium(II) iodide

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Ytterbium(III) bromide

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Ytterbium(III) chloride

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Ytterbium(III) iodide

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Ytterbium(III) oxide

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Yttrium bromide

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Yttrium chloride

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Yttrium fluoride

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Yttrium iodide

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Yttrium phosphate

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Yttrium(III) oxide

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Zeise's salt

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Zinc bromide

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Zinc carbonate

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Zinc chloride

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Zinc dithionite

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Zinc fluoride

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Zinc hydroxide

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Zinc iodide

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Zinc nitrate

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Zinc oxide

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Zinc silicate

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Zinc sulfide

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Zirconium silicate

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Zirconium(II) bromide

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Zirconium(II) chloride

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Zirconium(III) bromide

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Zirconium(III) chloride

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Zirconium(III) iodide

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Zirconium(IV) bromide

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Zirconium(IV) chloride

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Zirconium(IV) fluoride

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Zirconium(IV) iodide

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Zirconium(IV) oxide

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Interactions and reactions classified as:
Type 23 Lewis Acid/Base Complexation Chemistry
      1 +4 1
      1 +3 1
      1 +1 1
      1 +3 1
      1 +3 1
      1 +4 1
      1 +2 +1
      1 +2 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +2 1
      1 +2 1
      1 +3 +5 1
      1 +2 1
      2 +3 1
      1 +2 1
      1 +2 1
      1 +3 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +2 1
      1 +1 1
      1 +4 1
      1 +4 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +1 1
      2 +1 1
      2 +1 1
      1 +1 1
      1 +1 1
      3 +1 1
      2 +1 1
      2 +1 1
      2 +3 1
      1 +1 1
      1 +2 1
      1 +3 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +1 1
      2 +1 1
      1 +1 1
      1 +2 1
      1 +3 1
      1 +1 1
      1 +2 1
      1 +2 1
      1 +2 1
      1 +1 1
      1 +1 1
      1 +2 1
      1 +1 1
      1 +2 1
      1 +1 1
      1 +2 1
      1 +2 1
      1 +1 1
      1 +1 1
      1 +2 1
      1 +2 1
      3 +2 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +1 1
      2 +1 1
      1 +2 1
      1 +1 1
      1 +2 1
      1 +2 +6 1
      1 +2 1
      1 +1 1
      1 +2 1
      1 +1 1
      1 +1 1
      1 +1 1
      2 +1 1
      1 +1 1
      1 +2 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +1 1
      1 +2 1
      1 +2 1
      1 +2 1
      1 +1 1
      2 +3 1
      1 +2 +4 1
      1 +1 1
      1 +3 +1 1
      2 +1 1
      1 +2 1
      2 +3 1
      2 +3 1
       +
      1 +1 +2 +1 1
      1 +2 1
      1 +5 1
      4 +8 +1 +2 4 +4
      4 +8 +1 +2 4 +4
      1 +2 1
      1 +2 1
      1 +2 1
      1 +4 1
      1 +8 1 +2 +4
      1 +1 1
      2 +8 1
      1 +2 1
      1 +2 1
      1 +2 1
      1 +4 1
      1 +6 1
      1 +6 1 +1
      1 +1 1
      1 +1 1 +6
       +
       +
       +
      1 +1 1 +2
      1 +2 1
      1 +2 1
      1 +2 1
      1 +6 1
      1 +6 1
      1 +6 1
      1 +6 1
      1 +6 1 +6
      1 +6 1
      1 +4 1 +4
      1 +4 1
      1 +4 1
      1 +4 1 +6
      1 +4 1 +6
      1 +3 1
      1 +3 1 +6
      1 +1 1 +6
      1 +3 1 +6
      1 +3 1
      1 +3 1 +6
      1 +3 1
      1 +1 1 +1
      1 +4 +2 1
      1 +6 1
      1 +6 1
      1 +2 + 1 +1
      1 +1 +1 1
      1 +2 1
      1 +3 +3 1
      1 +3 1
      1 +7 2 +3
      1 +4 1 +4 +6
      1 +2 1 +1
      1 +1 + 1 +2 +1
      1 +2 + 1 +4 +1
      1 +2 + 1 +2 +1
      1 +1 +1 + 1 +2 +1
      1 +3 1
      1 +1 1 +6
      1 +1 1
      1 +2 1 +2
      1 +4 1
      1 +2 1
      1 +2 1 +1
      1 +1 +1 +1 + 1 +1 +1
      1 +1 +1 +1 + 1 +1 +1
      1 +1 +1 +1 + 1 +1 +1
      2 +1 + 1 +2
      2 +2 +2 +1 + 1 +2 +2
      2 +1 1
      1 +1 +1 +1 + 1 +1 +1
      1 +1 + 1
      1 +1 + 1
      1 +2 + 1 +1
      1 +2 1
      1 +2 + 2 +1 +2
      1 +5 1
      1 +2 + 2 +1 +2
      2 +4 + 2 +1
      1 +2 + 1 +2



Poster
Nucleophiles & Bases

© Mark R. Leach 1999-


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