Chapter 9 Lecture 1 Coordination Chemistry Structure History of Coordination Chemistry Definitions Coordination Compound = new chemical compounds formed by the binding of simpler, yet distinct, molecules by non-covalent bonds Simple Covalent Bond = bond formed by the sharing of one electron from each member. H3C• + •H H3C—H Coordinate Covalent Bond = bond formed by the donation of both electrons from one member. H3N: + Ni2+ Ni2+—NH3 Other non-covalent interactions Hydrogen Bonding p-p bonds

Early theory of coordination compound structure Ligand = atom, ion, or molecule that can donate a pair of electrons to a metal ion (A Lewis Base) = H2O, NH3, Cl- Werner Complexes Alfred Werner (1866-1919) was the father of modern coordination chemistry Early theory of coordination compound structure Blomstrand (1826-1894) and Jorgenson (1837-1914) The “valence” or charge of the metal ion determined how many bonds it could form: Co3+ could form 3 bonds This idea stressed the similarity to organic chemistry (C could form 4 bonds) NH3 could form chains, just like chains of CH2 Only Cl- attached to an NH3 could dissociate Evidence: -Amount of AgCl precip -Conductance Value

Werner’s Theory Metals interact with 6 ligands in octahedral geometry to form “complex ions” Primary or Inner Coordination Sphere = ligands with bonds to Metal Secondary or Outer Coordination Sphere = more loosely bound anions present only to balance charge Explains multiple complexes of the same sets of ligands in diff. numbers [Co(NH3)6]Cl3 [Co(NH3)5Cl]Cl2 [Co(NH3)4Cl2]Cl [Co(NH3)3Cl3] Different numbers of ions are produced due to outer sphere dissociation Explains multiple complexes with exact same formula = isomers Finally convinced Jorgenson by synthesizing both Optical Activity only possible for octahedral structure

Further ideas of Werner proved correct as well His use of “inert” or slow-reacting metal ions (Co3+, Cr3+, Pt2+) let him successfully isolate all of the isomers Coordination Number = the number of ligands a given metal ion prefers to have bound. Most first row transition elements prefer 6. Pt2+ prefers 4 = square planar geometry. CoA4B2 only has two isomers. Trigonal Prismatic and Trigonal Antiprimatic should give 3 isomers. Octahedral only has two possible isomers. Thus the structure must be Oh. PtA2B2 only has two isomers. It must be square planar rather than tetrahedral, which would only have 1 isomer. Water completes the Inner Sphere coordination in aqueous solutions: NiCl2 + H2O [Ni(H2O)6]Cl2 For his work on Coordination Chemistry, Werner was awarded the Nobel Prize in 1913

Nomenclature of Coordination Complexes Problem with Werner’s Theory: disobeys octet rule. Solution: use d-orbitals so it becomes an 18-electron rule. [Co(NH3)6]3+ has 6 d e- + 12 e- from NH3 1s + 3p + 5d orbitals x 2 e- each = 18 total electrons possible Nomenclature of Coordination Complexes Ligands Ligands are often organic molecules with IUPAC names Common names are most often used for the ligands in coordination compounds Chelate = Greek for Claw = a ligand that can bind a metal ion by more than one point of attachment. Bidentate = “two teeth” = NH2CH2CH2NH2 = ethylenediamene = en Tridentate = NH2CH2CH2NHCH2CH2NH2 = diethylenetriamine = trien Tetradentate = cyclam Table 9-2 lists common ligands, names, structures, and abbreviations

Naming and Writing Formulas of Coordination Compounds The cation comes first, then the anion(s) diamminesilver(I) chloride [Ag(NH3)2]Cl potassium hexacyanoferrate(III) K3[Fe(CN)6] Inner Sphere Complex Ion is enclosed in brackets Ligands are named before the metal Metal is written first in the formula A space only between cation and anion No capitalization is needed tetraamminecopper(II) sulfate [Cu(NH3)4]SO4 hexaamminecobalt(III) chloride [Co(NH3)6]Cl3 Prefixes denote the number of each ligand type. Special prefixes and parentheses are used if the ligand already contains a prefix. 2 di bis 6 hexa hexakis tri tris 7 hepta heptakis tetra tetrakis 8 octa octakis penta pentakis 9 nona nonakis 10 deca decakis

dichlorobis(ethylenediamine)cobalt(III) fluoride [Co(en)2Cl2]F tris(bipyridine)iron(II) chloride [Fe(bipy)3]Cl2 Ligands are named in alphabetical order not counting prefixes. tetraamminedichlorocobalt(III) [Co(NH3)4Cl2]+ amminebromochloromethylamineplatinum(II) [Pt(NH3)BrCl(CH3NH2)] Ligand name alterations: Anionic ligands are given an -o suffix: chloro, fluoro, oxo, sulfato Neutral ligands keep their name: methylamine, bipyridine Water becomes aqua NH3 becomes ammine to keep separate from alkylamines Two systems for showing charge or oxidation state of metal ion Stock system: oxidation state in Roman Numerals in parenthesis after the metal ion name. This is the most common method. Ewing-Basset system: charge of the total complex ion is placed in parenthesis after the name of the metal ion.

Both systems add –ate to the metal name if the complex ion has an overall (-) charge [Pt(NH3)4]2+ = tetraamineplatinum(II) or (2+) [PtCl4]2- = tetrachloroplatinate(II) or (2-) [PtCl6]2- = hexachloroplatinate(IV) or (2-) Isomer designations come before the rest of the name and in italics cis-diamminedichloroplatinum(II) trans-diamminedichloroplatinum(II) 8) Bridging ligands have the prefix m [(NH3)4Co(OH)(NH2)Co(NH3)4]4+ = m-amido-m-hydroxobis(tetraaminecobalt(III)) Negatively charged complexes of metals originally having Latin names: Fe = ferrate Ag = argenate Sb = stibate Au = aurate Pb = plumbate Sn = stannate Au = aurate Exception: Hg still called mercurate (Latin name: hydrargyrum)