Copyright © Houghton Mifflin Company. All rights reserved. 20a–1 Alfred Werner 1913 Nobel Prize in Chemistry Theory of the structure of coordination compounds
Copyright © Houghton Mifflin Company. All rights reserved. 20a–2 Werner's Coordination Theory primary valence => ion charge secondary valence => coordination number inner sphere => ligands bonded directly to metal ion outer sphere => next sheath of ions or molecules
Copyright © Houghton Mifflin Company. All rights reserved. 20a–3 Terminology coordinate covalent bond - covalent bond formed by one atom donated both electrons of shared pair; Lewis acid-base reaction ligand - electron pair donor; Lewis base coordination number - number of electrons pairs accepted by central metal atom
Copyright © Houghton Mifflin Company. All rights reserved. 20a–4 Coordinate Covalent Bond
Copyright © Houghton Mifflin Company. All rights reserved. 20a–5 Some Common Ligand
Copyright © Houghton Mifflin Company. All rights reserved. 20a–6 More Ligands
Some important aspects of transition metal ions: 1. The valence electrons are in d orbitals 2. The d orbitals do not have large radial extension 3. The d orbitals are therefore mostly nonbonding in complexes of transition metal ions 4. For these reasons, the effects of redox changes are substantially smaller for transition metals than for main group elements
Copyright © Houghton Mifflin Company. All rights reserved. 20a–8
Copyright © Houghton Mifflin Company. All rights reserved. 20a–9
Copyright © Houghton Mifflin Company. All rights reserved. 20a–10 Coordination Compounds: Structure and Nomenclature Coordination Number => 2, 4 & 6 most common CN Shape 2 linear 4 tetrahedral 4square planar 6 octahedral
Copyright © Houghton Mifflin Company. All rights reserved. 20a–11 Coordination Number 2
Copyright © Houghton Mifflin Company. All rights reserved. 20a–12 Coordination Number 4
Copyright © Houghton Mifflin Company. All rights reserved. 20a–13 Coordination Number 6
Copyright © Houghton Mifflin Company. All rights reserved. 20a–14 Multiplicity Monodentate mono => 1 di => 2 tri => 3 tetra => 4 penta => 5 hexa => 6 Bi- or tri- dentate bis => 2 tris => 3 tetrakis => 4
Names 1. In naming the entire complex, the name of the cation is given first and the anion second (just as for sodium chloride), no matter whether the cation or the anion is the complex species. 2. In the complex ion, the name of the ligand or ligands precedes that of the central metal atom. (This procedure is reversed from writing formulae.) 3. Ligand names generally end with 'o' if the ligand is negative ('chlorido' for Cl-, 'cyanido' for CN-, 'hydrido' for H-) and unmodified if the ligand is neutral ('methanamine' for MeNH2). Special ligand names are 'aqua' for water, 'ammine' for ammonia, 'carbonyl' for CO, 'nitrosyl' for NO.
Copyright © Houghton Mifflin Company. All rights reserved. 20a–16 4. A Greek prefix (mono, di, tri, tetra, penta, hexa, etc.) indicates the number of each ligand (mono is usually omitted for a single ligand of a given type). If the name of the ligand itself contains the terms mono, di, tri, eg triphenylphosphine, then the ligand name is enclosed in parentheses and its number is given with the alternate prefixes bis, tris, tetrakis instead. For example, NiCl2(PPh3)2 is named dichloridobis(triphenylphosphane)nickel(II). Again, one would use diammine, for (NH3)2, but bis(methylamine), for (NH2Me)2, to make a distinction from dimethylamine. (Note that this ambiguity does not arise if the preferred IUPAC name, methanamine, is used instead of methylamine). There is no elision of vowels or use of a hyphen, e.g. in tetraammine and similar names. Some texts suggest that if a ligand is "complicated" then use the bis, tris multipliers. What constitutes "complicated" is not spelled out however, so a simpler approach is to use them if the name of the ligand is three or more syllables long!
Copyright © Houghton Mifflin Company. All rights reserved. 20a–17 5. A Roman numeral or a zero in parentheses is used to indicate the oxidation state of the central metal atom. 6. If the complex ion is negative, the name of the metal ends in 'ATE' for example, ferrate, cuprate, nickelate, cobaltate etc. 7. If more than one ligand is present in the species, then the ligands are named in alphabetical order regardless of the number of each. For example, NH3 (ammine) would be considered an 'a' ligand and come before Cl- (chlorido). (This is where the 1971 rules differed from the 1959 rules. Some texts still say that ligands are named in the order: neutral then anionic). Examples: [Co(en)3]Cl3 [Co(NH3)3(NO2)3] K2[CoCl4] note that it is not necessary to enclose the halogens in brackets
Copyright © Houghton Mifflin Company. All rights reserved. 20a–18 Nomenclature Neutral molecule [Ru(NH 3 ) 4 (HSO 3 ) 2 ] bis(bisulfite)tetraamineruthenium(II)
Copyright © Houghton Mifflin Company. All rights reserved. 20a–19 Nomenclature Anionic coordination sphere K 3 [Fe(CN) 6 ] potassium hexacyanoferrate(III)
Copyright © Houghton Mifflin Company. All rights reserved. 20a–20 Nomenclature Cationic coordination sphere [Cu(NH 3 ) 4 ]SO 4 tetraaminecopper(II) sulfate
Copyright © Houghton Mifflin Company. All rights reserved. 20a–21 Nomenclature Cationic coordination sphere & Anionic coordination sphere [Ti(H 2 O) 6 ][CoCl 6 ] hexaaquatitanium(III) hexachlorocobaltate(III)
Copyright © Houghton Mifflin Company. All rights reserved. 20a–22 Coordination Isomers [Co(NH 3 ) 6 ][Cr(CN) 6 ] [Cr(NH 3 ) 6 ][Co(CN) 6 ]
Copyright © Houghton Mifflin Company. All rights reserved. 20a–23