《无机化学》课件-171_chapter20-transitionmetals(I)-lecture1.pptVIP

Chapter 20 Transition metals (I) 20-1 Introduction 20-1 Introduction 20-1 Introduction 20-1 Introduction 20-1 Introduction 20-1 Introduction 20-1 Introduction 1) Color: The complexes of the d-block metal ions are usually colored, except, very often, those of d0 and d10 metal ions. The colors are due to: a) electronic transitions of d-electrons within the d sub-shell. These are known as d→d transitions. d0 and d10 metal ions do not show these transitions. b) electronic transitions from the metal ion to the ligand (M→L transitions) or ligand to the metal ion (L→M transitions), which are known as charge-transfer transitions, and these can occur for d0 to d10 metal ions. c) The ligands themselves may be colored, and this color may contribute to the color of the complex.20-1 Introduction 2) Paramagnetism: When there are unpaired electrons in the d sub-shell, these will lead to paramagnetism. Thus, in [Cr(H2O)6]3+ the three d electrons (it is d3) are unpaired. Thus, like the O2 molecule which is paramagnetic, Cr(III) is paramagnetic. A d10 metal ion (e.g. Zn(II)) has a filled d sub-shell, and a d0 metal ion (e.g. Ti(IV)) has no d-electrons, so neither of these can be paramagnetic. 20-1 Introduction Oxidation states of first-row d-block ions:Sc Ti V Cr Mn Fe Co Ni Cu Zn 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 23 3 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 5 5 5 5 6 6 6 7 The most stable oxidation states are in red, rarer oxidation states pale blue:These achievethe groupoxidation stateThe higher oxidat-ion states become progressIvely less stable as the divalent state becomes dominantMaximum at Mn(VII) 3 4 5 6 7 8 9 10 11 12 20-1 Introduction The three Group 4 elements that occur naturally are titanium (Ti), zirconium (Zr) and hafnium (Hf). The first three members of the group share similar properties; all three are hard refractory metals under standard conditions. However