Effects of the 3d & 4s Subshells on Oxidation States of the Transition Elements * Transition elements can have variable oxidation states * These variable oxidation states can be formed as the 3d and 4s atomic orbitals are similar in energy * This means that a similar amount of energy is needed to remove a different number of electrons * When the transition elements form ions, the electrons of the 4s subshell are lost first, followed by the 3delectrons * The most common oxidation state is +2, which is usually formed when the two 4s electrons are lost Oxidation number at the start of the 3d transition elements + Atthe start of the period, it is easier for the transition elements to lose the maximum number of electrons * The maximum oxidation number of these transition elements involves all the 4s and 3d electrons in the atom + Forexample, the maximum oxidation state of a titanium (Ti) ionis +3 or +4, as two 4s electrons and either] or 23d electrons are lost * Tiatom=s? 2s? 2p* 3s? 3p 3d? 4s? © Ti5+ion=1s? 2s? 2p 3s? 3p%3d! © Tit ion = 1s? 2s? 2p$ 3s? 3p6Oxidation number at the end of the 3d transition elements. * Towards the end, the 3d transition elements are more likely to adopt the +2 oxidation state + Thisis because across the d block, the 3d electrons become slightly harder to remove as the nuclear charge increases © The delectrons are attracted more strongly to the nucleus © The higher oxidation states become less stable * Therefore, the elements are more likely to lose their 4s electrons only * For example, nickel (Ni)is a transition element at the end of the period which only forms ions with oxidation state +2, due to loss of the 4s electrons only © Niatom=1s# 2s 2p® 3s? 3p® 3d® 4s? o Ni2tion=1s*2s?2p® 3s? 3p®3d®Transition Elements: Catalysts * Transition elements are often used as catalysts due to their ability to formions with more than one stable oxidation state, and the fact that they contain vacant d orbitals Oxidation states * Transition element ions can adopt more than one stable oxidation state * This means that they can accept and lose electrons easily to go from one oxidation state to another + They can therefore catalyse redox reactions, by acting as both oxidising agents and reducing agents + For example, iron (Fe) is often used asa catalyst due to its ability to form Fe(|l) and Fe(lll) ions, acting as an oxidising agent and a reducing agent © When Fe(ll) acts as a reducing agent, it will reduce another species and become oxidiseditself Fe2++ Fedt + e- + The Fe?* formed in the catalytic cycle, can then also act as an oxidising agent by oxidising another species and getting reduced itself to reform the Fe** ion Fe3+ +e-— Fe? * Transition elementions with high oxidation states make powerful oxidising agents, because they will readily accept electrons © Acommon example of this is potassium permanganate (VII), where manganese has an oxidation state of +7Vacant d orbitals * When transition elements form ions, they have vacant d orbitals which are energetically accessible © The orbitals are not too high in energy + This means that dative bonds can be formed between the transition element ion and ligands ° Eachligand provides the pair of electrons required for the formation of a bond between the ion andthe ligand © This pair of electrons is donated into the ion's vacant d orbital * The table below shows the electron configuration of the transition element atoms * When they form ions, empty d orbitals are obtained which can be filled by the pairs of electrons donated by the ligandsElectronic configuration of transition elements table ata Electronic Configuration 162 25202 penss2rsp® 3d? 42 4s2 2s? 2p® 3s? 3p® 3d° 4s" 4s? 25? 2p® 35? 3p® 3d° 4s? 4s? 2s? 2p? 3s? 3p® 3d’ 4s? 4s? 2s? 2p® 3s? 3p® 3d° 4s? 4s? 2s? 2p® 3s? 3p® 3d® 45? 4s? 2s? 2p® 352 3p 3d” As!Transition Metals: Complex ons Acomplexis a molecule or ion formed by a central metal atom orion surrounded by one or more ligands © Acomplexcan have an overall positive ornegative charge, orit can be neutral © Ifacomplexis charged overall, itis often called a complexion Transition elements can easily for complex ions, because they have empty d orbitals that are energetically accessible © The empty d orbitals are theretore not too high in energy and can accommodate alone pair of electrons The transition elementin the centre will accept pairs of electrons from the ligands into their empty d orbitals, forming dative bonds © Thetransition element in the centre is often referred to as the central metalion, asall transition elements are metals, and it is often anion in the centre Forexample, the titaniumilil) (Ti?*) ion, has an electronic configuration of Is*2s*2p* 3s” 3p°3d! © This means that there are vacant d orbitals that canbe occupied by electrons, from ligands such as HO for example, to forma [Ti(H20),]* complexion © 4waterligands have each donated a pair of electrons, to form 6 dative bonds with the central metalionTransition Elements: Ligands & Complex Formation * Transition element ions can form complexes which consist of a central metal ion and ligands * Copper(ll) and cobalt(ll) ions will be used as examples of the central metal ions, inthe complex formation with water (H20), ammonia (NH3), hydroxide (OH), and chloride (CI) ligands © Acoppet(ll) ion has an electronic configuration of 1s22s*2p%3s?3p3d? © Acobalt(ll) ion has an electronic configuration of 1s*2s72p*3s?3p°3d7Complexes with water & ammonia molecules Water and ammonia molecules are examples of neutral ligands Both ligands contain alone pair of electrons which can be used to form a dative covalent bond with the central metalion 2 Inwater, thisis the lone pairon the oxygen atom 2 Inammonia, itis the lone pair on the nitrogen atom Since water and ammonia are smallligands, 6 of them can fit around a central metalion, each donating a lone pair of electrons, forming 6 dative bonds © The coordination number of a complexis the number of dative bonds formed between the central metalionand the ligands © Since there are 6 dative bonds, the coordination number for the complexis 6 ‘Complexes with a coordination number of 6 have an octahedral shape The overall charge of a complexis the sum of the charge on the central metal ion, and the charges on each of the ligands Acomplex with cobaltill) or copper(ll) as a central metalion, and water orammonia molecules as ligands, will have an overall charge of 2+ © The central metalion has a 2+ charge and the ligands are neutral- . 42+ 2QH, HO: \ | i ‘OH, Cu H,0 J t \ ‘OH. L OH, L OCTAHEDRAL OCTAHEDRAL OVERALL CHARGE = 2+ OVERALL CHARGE = 2+ - 72+ - 742+ NH, NH, HNL a me ae E Nai, ne ® \ NH, NH, OCTAHEDRAL OCTAHEDRAL OVERALL CHARGE = 2+ OVERALL CHARGE = 2+ Cobalt(Il) and copper(I!) form octahedral complexes with ammonia and water ligandsComplexes with hydroxide & chloride ions * Hydroxide and chloride ions are examples of negatively charged ligands Both ligands contain a lone pair of electrons which canbe used to form a dative covalent bond with the central metal ion Hydroxide ligands are small, so 6 of them can fit around a central metalion and the complex formed will have a coordination number of 6 Chloride ligands are large ligands, so only 4 of them will ft around a central metal ion Complexes with 4 chloride ligands will have a coordination number of 4 © Complexes with 4 chloride ligands will form tetrahedral complexes © Whereas hydroxide ligands will form octahedral complexes Acomplex with cobalt(II) or copper(|l) as a central metal ion and chloride ions as ligands, will have an overalll charge of 2- © The central metal ion has a charge of 2+ © Eachchloride ligand has a charge of 1- © There are 4 chloride ligands in the complex, so the overall negative charge is 4~ © The overall positive charge is 2+ © Therefore, the overall charge of the complexis 2~ + Acomplexwith cobalt(ll) or copper(ll) as a central metal ion and hydroxide ions as ligands, will have no overall charge The central metalion has a charge of 2+ Each hydroxide ligand has a charge of I~ There are 2 hydroxide ligands in the complex, so the overall negative charge is 2- The overall positive chargeis 2+ Therefore, the overall charge on the complexis O2- 2- t i Cu Co oi” t Na af” t Nei cl cl TETRAHEDRAL TETRAHEDRAL (OVERALL CHARGE = 2-) (OVERALL CHARGE = 2-) QH H,0: | :OH, NYS 40:7 . on, OH QH H,0% | 30H, NYY 40:7 ‘ von, 6H OCTAHEDRAL (OVERALL CHARGE = 0) OCTAHEDRAL (OVERALL CHARGE = 0) Cobalt(Il) and copper(il) form tetrahedral complexes with chloride and octahedral complexes with water and hydroxide ligandsDefine Ligand * Aligand is a molecule orion that has one or more lone pairs of electrons * These lone pairs of electrons are donated by the ligand, to form dative covalent bonds to a central metalatomorion Examples of ligands table Name of Ligand Formula of LigandQH, 2+ H,O% | 20H, NLL 40:7 \ oon, OH 12 Example of a complex formed between transition metal ion (Fe?) and a ligand (HO) by dative covalent bonds Types of Ligands ‘© Different ligands can form different numbers of dative bonds to the central metal ion in a complex. © Some ligands can form one dative bond to the central metal ion © Other ligands can form two dative bonds, and some can form multiple dative bonds Monodentate ligands ‘* Monodentate ligands can form only one dative bond to the central metal ion * Examples of monodentate ligands are: © Water (H,0) molecules © Ammonia (NHs) molecules © Chloride (CIyions © Cyanide (CN’) ions[ a 4.9 ae Cu a i Na Ho” ‘ \ CL Hy 6 — tcc FetH,0),1* NH, C 7 HN? ‘ NH. NC: 2CN ‘\ Cu “ ° ‘\ Ni “x Hn” t Nun, ne” Neon NH, — [Cu(NH,),]°* - — ENi(CN}]7 Examples of complexes with monodentate ligandsBidentate ligands * Bidentate ligands can each form two dative bonds to the central metalion * Thisis because each ligand contains two atoms with lone pairs of electrons * Examples of bidentate ligands are: © 1,2-diaminoethane (H2NCH2CH2NHo) which is also written as ‘en’ © Ethanedioate ion (C204*") whichis sometimes written as ‘ox’ 2+ tCufen),!"*" [Co(C,0),17 Examples of complexes with bidentate ligandsPolydentate ligands * Some ligands contain more than two atoms with lone pairs of electrons © These ligands can form more than two dative bonds to the and are said to be polydentate ligands * An example of a polydentate ligand is EDTA* , which is a hexadentate ligand as it forms 6 dative covalent bonds to the central metalion oO Q a= oR 0 oy P o Yo i cu NN —= C Opp Oened o ~O 9°, ° on ; ° EDTA LIGAND COPPER (II) — EDTA COMPLEX Example of a polydentate ligand complex