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2015 NOMENCLATURE Nomenclature Ligands are frequently named using older trivial names rather than the International Union of Pure and Applied Chemistry (IUPAC) names. Table 1 list common ligands. Those with two or more points of attachment to metal atoms are called chelating ligands, and their compounds are called chelates (pronounced key-lates), a name derived from the Greek khele, the claw of a crab. Ligands such as ammonia are monodentate, with one point of attachment (literally, “one tooth”). Ligands are described as bidentate if they have two points of attachment, as in ethylenediamine (NH2CH2CH2NH2), which can bond to metals through the two nitrogen atoms. The prefixes tri-, tetra-, penta-, and hexa- are used for three through six bonding positions (Table 2). Chelate rings may have any number of atoms; the most common contain five or six atoms, including the metal. Smaller rings have angles and distances that lead to strain; larger rings frequently result in crowding, both within the ring and between adjoining ligands. Some ligands form more than one ring; ethylenediaminetetraacetate (EDTA) can form five via its carboxylate groups and two amine nitrogen atoms. Table 1 Common Name hydrido fluoro chloro bromo IUPAC Name hydrido fluoro chloro bromo Formula H F Cl Br iodo nitrido azido oxo iodo nitrido azido oxido cyano thiocyanato-S(S-bonded) I N3 N 3 O2 CN SCN cyano thiocyano Inorganic Chemistry B 1 2015 NOMENCLATURE isothiocyano hydroxo isothiocyanato-N(N-bonded) hydroxo aqua carbonyl thiocarbonyl nitrosyl nitro nitrito aqua carbonyl thiocarbonyl nitrosyl nitrito -N (N-bonded) nitrito- O (O-bonded) methylisocyanide phosphine methylisocyanide phosphane pyridine ammine methylamine amido imido pyridine (abbrev. py) ammine methylamine azanido azanediido Inorganic Chemistry B NCS OH H2O CO CS NO+ NO2 ONO CH3NC PR3 C5H5N NH3 MeNH2 NH2 NH2 2 2015 NOMENCLATURE Table 2 Inorganic Chemistry B 3 2015 NOMENCLATURE Inorganic Chemistry B 4 2015 NOMENCLATURE Nomenclature Rules 1. The cation comes first, followed by the anion. Examples: diamminesilver(I) chloride, [Ag(NH3)2]Cl potassium hexacyanoferrate(III), K3[Fe(CN)6] 2. The inner coordination sphere is enclosed in square brackets. Although the metal is provided first within the brackets, the ligands within the coordination sphere are written before the metal in the formula name. Examples: tetraamminecopper(II) sulfate, [Cu(NH3)4]SO4 hexaamminecobalt(III) chloride, [Co(NH3)6]Cl3 3. The number of ligands of each kind is indicated by prefixes (Table 3). In simple cases, the prefixes in the second column are used. If the ligand name already includes these prefixes or is complicated, it is set off in parentheses, and prefixes in the third column (ending in –kis) are used. Examples: dichlorobis(ethylenediamine)cobalt(III), [Co(NH2CH2CH2NH2)2Cl2]+ tris(2,2-bipyridine)iron(II), [Fe(C10H8N2)3]2+ Table 3 2 di bis 3 4 5 6 7 8 9 10 tri tetra penta hexa hepta octa nona deca tris tetrakis pentakis hexakis heptakis octakis nonakis decakis Inorganic Chemistry B 5 2015 NOMENCLATURE 4. Ligands are generally written in alphabetical order according to the ligand name, not the prefix. Examples: tetraamminedichlorocobalt(III), [Co(NH3)4Cl2]+ (tetraammine is alphabetized by a and dichloro by c , not by the prefixes) amminebromochloromethylamineplatinum(II), Pt(NH3)BrCl(CH3NH2) 5. Anionic ligands are given an o suffix. Neutral ligands retain their usual name. Coordinated water is called aqua and coordinated ammonia is called ammine . Examples are in Table 1. 6. Two systems exist for designating charge or oxidation number: a. The Stock system puts the calculated oxidation number of the metal as a Roman numeral in parentheses after the metal name. Although this is the most commonly employed method, its drawback is that the oxidation state of a metal within a complex can be ambiguous, and difficult to specify. b. The Ewing-Bassett system puts the charge on the coordination sphere in parentheses after the name of the metal. This convention offers an unambiguous identification of the species. In either case, if the charge is negative, the suffix -ate is added to the name. Examples: tetraammineplatinum(II) or tetraammineplatinum(2+), [Pt(NH3)4]2+ tetrachloroplatinate(II) or tetrachloroplatinate(2–), [PtCl4]2 hexachloroplatinate(IV) or hexachloroplatinate(2–), [PtCl6]2 7. Prefixes designate adjacent (cis -) and opposite (trans -) geometric locations. Other prefixes will be introduced as needed. Examples: cis - and trans -diamminedichloroplatinum(II), [PtCl2(NH3)2] cis - and trans -tetraamminedichlorocobalt(III), [CoCl2(NH3)4]+ Inorganic Chemistry B 6 NOMENCLATURE 2015 8. Bridging ligands between two metal ions (Figures 1) have the prefix -. Examples : tris(tetrammine--dihydroxocobalt)cobalt(6+), [Co(Co(NH3)4(OH)2)3]6+ -amido--hydroxobis(tetramminecobalt)(4+), [(NH3)4Co(OH)(NH2)Co(NH3)4]4+ Fig. Bridging Amide and Hydroxide Ligands in Fig. cis and trans Isomers of -amido--hydroxobis(tetraamminecobalt)(4+), Diamminedichloroplatinum(II), [PtCl2(NH3)2]. [(NH3)4Co(OH)(NH2)Co(NH3)4]4+. The cis isomer, also known as cisplatin, is used in cancer treatment. 9. When the complex is negatively charged, the names for these metals are derived from the sources of their symbols: iron (Fe) ferrate lead (Pb) plumbate silver (Ag) argentate tin(Sn) stannate gold (Au) aurate copper (Cu) cuprate Examples: tetrachloroferrate(III) or tetrachloroferrate(1–), [FeCl4] dicyanoaurate(I) or dicyanoaurate(1–), [Au(CN)2] Name these coordination complexes: a. Cr(NH3)3Cl3 b. Pt(en)Cl2 c. [Pt(ox)2]2 d. [Cr(H2O)5Br]2+ e. [Cu(NH2CH2CH2NH2)Cl4]2 f. [Fe(OH)4] Inorganic Chemistry B 7 2015 NOMENCLATURE Give the structures of these coordination complexes: a. Tris(acetylacetonato)iron(III) b. Hexabromoplatinate(2–) c. Potassium diamminetetrabromocobaltate(III) d. Tris(ethylenediamine)copper(II) sulfate e. Hexacarbonylmanganese(I) perchlorate f. Ammonium tetrachlororuthenate(1–) Inorganic Chemistry B 8