Specifically lectures 1-5 for the Coordination Chemistry course in Core Chemistry 1, Durham University Chemistry.
This is a very detailed set of notes with lots of examples and diagrams to consolidate what is taught from the text. It is very useful for any undergraduate taking an introductory c...
Complexes have applications in synthesis of organic compounds, analytical chemistry, dyes
paints and pigments, polymer (plastic) manufacture, homogenous catalysis
Complexes play vital roles in biological chemistry
E.g. haemoglobin (Fe heme), oxygen transport in red blood cells
Haemoglobin has Fe2+ centre
Square-based pyramid: 4 nitrogen atoms of porphyrin ring, nitrogen atom of
histidine residue on protein
Complexation of dioxygen in vacant coordination site
Other small molecules can bind to Fe centre e.g. CO
Binding of CO very strong toxic
Photosynthesis: chlorophyll
Photosynthesis: Photosystem II
A protein complex made of many subunits
Contains Mn4CaO5 cluster
Conversion of H2O to O2 – oxygen evolving complex (OEC)
Mn3+ and Mn4+ centres
Nitrogen fixation: conversion of N2 into NH3 or related compounds
Nitrogenase: catalyses reduction of dinitrogen to ammonia
N2 + 8H+ + 8e- NH3 + H2 (16 ATP 16 ADP)
, Synthetic nitrogen fixation: Haber process (Haber-Bosch process)
Industrial process which coverts dinitrogen to ammonia
N2 + 3H2 2NH3 Fe catalyst, 450 degrees celsius, 200 atm
Uses of NH3 = fertilisers, explosives, dyes
Current research: synthesis of transition metal complexes for nitrogen fixation, e.g., dinitrogen
complexes
Many Fe or Mo complexes
P and/or N donor ligands popular
Complexes are formed by the d-, f- and s-,
p- block elements
D-block elements: elements that possess d orbitals
i.e. all elements in groups 3-12
5-d orbitals, l = 2, ml = -2, -1, 0, +1, +2
L = angular momentum quantum number (0 – (n-1))
Ml = magnetic quantum number
Transition metal: an element with an unfilled d- or f- orbital (i.e.
partially filled d- or f- subshell) in a least one common oxidation state
E.g., copper, valence electron configuration: [Ar]4s13d10 (all d orbitals are filled)
Common oxidation states: Cu+ and Cu2+
Cu+ = [Ar]3d10 (all d orbitals are filled)
Cu2+ = [Ar]3d9
Therefore copper is both a d-block element and a transition metal
E.g., zinc, valence electron configuration: [Ar]4s 23d10 (all d orbitals are filled)
Common oxidation state: Zn2+
Zn2+ = [Ar]3d10 (all d orbitals are filled)
Therefore zinc is a d-block element, but not a transition metal
Alfred Werner investigated complexes containing cobalt, chlorine and ammonia
Alfred Werner investigated the reactivity of each compound with AgNO 3
Werner’s work gave rise to the three terms: complex (coordination compound), ligand,
coordination number (‘CN’)
Complex: positively charged central ion (or possibly a neutral atom), an acceptor, surrounded
in a symmetrical manner by a shell of ions or molecules called ligands
Acceptor: electrophile or Lewis acid (e- pair acceptor)
Ligand: nucleophile or Lewis base (e- pair donor)
A complex formally consists of: (see next page for useful diagrams)
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