Metal Complexes -- Chapter 24 Metal Complex -- consists of a set of ligands that are bonded to a central metal ion by coordinate covalent bonds. e.g. Cu2+ + 4 L --> [CuL4]2+ ( L = NH3, H2O, etc) Ligands are Lewis Bases and can be: monodentate -- one donor atom e.g. H2O, NH3, Cl–, OH–, etc. bidentate -- two donor atoms e.g. ethylenediamine, NH2–CH2–CH2–NH2 “en”

Polydentate ligands = EDTA4– polydentate -- more than two donor atoms e.g. EDTA -- ethylenediaminetetraacetic acid (6 donor atoms) = EDTA4–

Chelate Effect Chelate effect -- complexes with bi- or polydentate ligands are more stable than those with similar monodentate ligands e.g. [Ni(en)3]3+ is more stable than [Ni(NH3)6]3+ Know Table 24.2!

Writing Formulas of Complex Ions Metal ion first, then ligands. Charge outside brackets. total charge = sum of metal ion + ligands e.g. metal ion ligand complex Cu2+ H2O [Cu(H2O)]2+ Co3+ NH3 [Co(NH3)6]3+ Fe3+ CN– [Fe(CN)6]3–

Nomenclature 1. Name the ligands, put in alphabetical order. 2. Add prefixes for ligands that appear more than once. 3. Name the metal Cationic complex; metal name Anionic complex; metal prefix + ate 4. Add oxidation state in roman numerals 5. As separate word, write “ion” if not neutral, or list counterions (positive first, negative second). Examples: Complex Name [Ni(CN)4]2– tetracyanonickelate(II) ion [CoCl6]3– hexachlorocobaltate(III) ion [CoCl2(NH3)4]+ tetraaminedichlorocobalt(III) ion Na3[Co(NO2)6] sodium hexanitrocobaltate(III) [CrCl2(en)2]2SO4 dichlorobis(ethylenediamine)chromium(III) sulfate

Coordination Number and Structure Coordination # -- number of donor atoms attached to the metal center (a) Two-Coordinate Complexes -- linear structures Rare except for Ag+ e.g. [Ag(NH3)2]+ and [Ag(CN)2]– (b) Four-Coordinate Complexes -- two structural types Tetrahedral structures -- common for ions with filled d subshells, e.g. Zn2+ as in [Zn(OH)4]2–

More Coordination Number and Structure (b) Four-Coordinate Complexes -- two structural types square planar structures -- common for d8 metal ions (Ni2+, Pd2+, Pt2+) and for Cu2+ e.g. (c) Six-Coordinate Complexes -- the most common! “always” octahedral structures, e.g.

Sample Problem 1. Give the name or formula, as required. Draw the structure of each complex. a) [AgI2]– b) [Co(en)3]3+ c) cis-dichlorobis(ethylenediamine)cobalt(III) chloride d) sodium tetracyanonickelate(II)

Answer 1. a) diiodoargentate(I) ion [I—Ag—I]– b) tris(ethylenediamine)cobalt(III) ion c) cis-[CoCl2(en)2]Cl c) Na2[Ni(CN)4]

Structural Isomers of Coordination Complexes Linkage isomers Coordination isomers pentaamminenitrocobalt(II) ion pentaamminenitritocobalt(II) ion pentaamminechlorocobalt(II) bromide pentaamminebromocobalt(II) chloride

Isomerism; Overview

Stereoisomers of Coordination Complexes (a) Geometrical Isomers cis trans fac mer (b) Enantiomers Three common ways to get enantiomers: --chiral ligand --tetrahedral complex with 4 different groups --octahedral complexes with chelating ligands (and no mirror plane)

Sample Questions Draw a clear, 3-dimensional structure of the geometrical isomer of Co(en)(NH3)2Cl2 that is optically active. (define any abbreviations) Excess silver nitrate is added to a solution containing 0.0522 mol of [Co(NH3)4Cl2]Cl. How many g of AgCl (FW = 143.3) will precipitate?

Sample Questions Draw a clear, 3-dimensional structure of the geometrical isomer of Co(en)(NH3)2Cl2 that is optically active. (define any abbreviations) Excess silver nitrate is added to a solution containing 0.0522 mol of [Co(NH3)4Cl2]Cl. How many g of AgCl (FW = 143.3) will precipitate? 7.48 g

Crystal Field Theory (Bonding in Transition Metal Complexes) Metal complexes are usually highly colored and are often paramagnetic -- such facts can be explained by a “d-orbital splitting diagram” eg dz2 dx2-y2 energy D = crystal field splitting energy t2g dxy dxz dyz d orbitals of the metal ion in an octahedral field of ligands d orbitals of the free metal ion

Shape and Directionality of the d Orbitals eg D t2g

Crystal Field Strength The size of D depends on… The nature of the ligand (ligand-metal bond strength!) “spectrochemical series” -- D decreases: CN– > NO2– > en > NH3 > H2O > OH– > F– > Cl– > Br– “strong field ligands” “weak field ligands” The oxidation state of the metal (charge!) D is greater for M3+ than for M2+ The row of the metal in the periodic table (size!) for a given ligand and oxidation state of the metal, D increases going down in a group e.g. D is greater in Ru(NH3)63+ than in Fe(NH3)63+ Colors of metal complexes are due to electronic transition between the t2g and eg energy levels

d Orbital Splitting Diagrams for Octahedral Complexes eg dx2 dx2–y2 eg dx2 dx2–y2 large D “low spin” small D “high spin” t2g t2g dxy dxz dyz dxy dxz dyz Fe(H2O)62+ Fe(CN)64–

High Spin vs. Low Spin CN– is a stronger field ligand than is H2O which leads to a greater D value (i.e. a greater d orbital splitting) As a result, Fe(H2O)62+ is a “high spin” complex and is paramagnetic (4 unpaired electrons) while, Fe(CN)64– is a “low spin” complex and is diamagnetic (no unpaired electrons) The CN– complex with the larger D value absorbs light of higher energy (i.e. higher frequency but shorter wavelength) OMIT … d orbital splitting diagrams for other geometries (i.e. tetrahedral and square planar)

Sample Questions A complex [CoA6]3+ is red. The complex [CoB6]3+ is green. a) Which ligand, A or B, produces the larger crystal field splitting D? b) If the two ligands are ammonia and water, which is A and which is B? c) Draw the d orbital diagram of either complex, assuming it is “high spin.” How many unpaired electrons will it have? Give the order of increase of D in the following sets: a) Cr(NH3)63+, CrCl63–, Cr(CN)63– b) Co(H2O)62+, Co(H2O)63+, Rh(H2O)63+

Sample Questions A complex [CoA6]3+ is red. The complex [CoB6]3+ is green. a) Which ligand, A or B, produces the larger crystal field splitting D? b) If the two ligands are ammonia and water, which is A and which is B? c) Draw the d orbital diagram of either complex, assuming it is “high spin.” How many unpaired electrons will it have? a) A b) A = NH3, B = H2O c) 4 unpaired electrons Give the order of increase of D in the following sets: a) Cr(NH3)63+, CrCl63–, Cr(CN)63– b) Co(H2O)62+, Co(H2O)63+, Rh(H2O)63+ a) Cr(CN)63– > Cr(NH3)63+ > CrCl63– b) Rh(H2O)63+ > Co(H2O)63+ > Co(H2O)62+ dz2 dx2-y2 eg dxy dxz dyz t2g