Covalent compounds, oxidation numbers

A peroxide oi peioxo compound contains at least one pair of oxygen atoms, bound by a single covalent bond, in which each oxygen atom has an oxidation number of —. The peroxide group can be attached to a metal, M, through one (1) or two (2) oxygen atoms, or it can bridge two metals (3) ... 

The transition metals, unlike those in Groups 1 and 2, typically show several different oxidation numbers in their compounds. This tends to make their redox chemistry more complex (and more colorful). Only in the lower oxidation states (+1, +2, +3) are the transition metals present as cations (e.g., Ag+, Zn2+, Fe3+). In higher oxidation states (+4 to +7) a transition metal is covalently bonded to a nonmetal atom, most often oxygen. 

In compounds, mercury has the oxidation number +1 or +2. Its compounds with oxidation number +1 are unusual in that the mercury(I) cation is the covalently bonded diatomic ion (Hg—Hg)2+, written Hg22+. 

In a covalent compound of known structure, the oxidation number of each atom is the charge remaining on the atom when each shared electron pair is assigned completely to the more electronegative of the two atoms sharing it. A pair shared by two atoms of the same element is split between them. 

H3 PO4 Phosphoric acid is a covalent compound with a net charge of zero. Each hydrogen atom has an oxidation number of+1 (Guideline 3), and each oxygen has an oxidation number of-2 (Guideline 4). Now add the contributions from these atoms 3(+l) + 4(-2) = -5. For the oxidation numbers to sum to zero (Guideline 2), the phosphorus atom of phosphoric acid must have an oxidation number of +5. 

We learned to write formulas of ionic compounds in Chaps. 5 and 6. We balanced the charges to determine the number of each ion to use in the formula. We could not do the same thing for atoms of elements in covalent compounds, because in these compounds the atoms do not have charges. In order to overcome this difficulty, we define oxidation numbers, also called oxidation states. 

N.N. Greenwood Whether your compounds are described as hyper-closo or iso-closo depends on the number of electrons assumed to be contributed by the metal atom to the cluster. If, as is generally assumed, ruthenium contributes two electrons to the cluster in compounds such as yours, then RUC2B7 has a closo 22e skeltal electron count (i.e. 2n+2) rather than a 20e hyper-closo count. The uncertainty concerning the most appropriate choice of formal oxidation state for metals in covalent compounds permeates... 

Stable binary ionic compounds are formed from ions that have noble gas configurations. None of the compounds meet this requirement. First of all, C04 is not an ionic compound at all because it is a covalent compound, made from 2 nonmetals. Even so, C04 is not stable because with O2, C would have an oxidation number of +8, which is very unlikely. Consider the following ionic compounds composed of a metal and... 

Unfortunately, many compounds contain bonds that are a mixture of ionic and covalent. In such a case, a formal charge as written is unlikely to represent the actual number of charges gained or lost. For example, the complex ferrocyanide anion [Fe(CN)6]4- is prepared from aqueous Fe2+, but the central iron atom in the complex definitely does not bear a +2 charge (in fact, the charge is likely to be nearer +1.5). Therefore, we employ the concept of oxidation number. Oxidation numbers are cited with Roman numbers, so the oxidation number of the iron atom in the ferrocyanide complex is +11. The IUPAC name for the complex requires the oxidation number we call it hexacyanoferrate (II). 

Hydrazotc acid, HN,. ply.. = 4.72, and most of its covalent compounds (including its heavy metal salts) are explosive. It is formed (1) in 90% yield by reaction of sodium amide with nitrous oxide, (2) by reaction of hydraztntum ion with nitrous acid, (3) by oxidation of hydrazimum salts, (4) by reactio n of hydt azinium hydrate with nitrogen trichloride tin benzene solution). Hvdrazoic acid forms metal azides with the corresponding hydroxides and carbonates. It reacts with HC1 to give ammonium chlonde and nitrogen, with H2SO4 to form hydrazinium acid solfate, with benzene to form aniline, and it enters into a number of oxidation-reduction reactions. 

OXIDATION NUMBER. In its original and restrictive sense, the number of electrons which must be added to a cation to neutralize the charge. The concept has been extended to anions by assignments of negative oxidation numbers. Moreover, it has been further extended, first to all atoms or radicals joined by electrovalent bonds, and then to covalent compounds in which the shared electrons are distributed equally. For the broadest use of the concept, the expression oxidation state is often used. 

Based on the foregoing experimental results, the versatility of metal carbonyls and their derivatives in their reactions with liquid NH3 may be summarized as follows (/) substitution of CO or other ligands by NH3 without change in the oxidation number of the transition metal in question (2) conversion of covalent carbonyl complexes into ionic compounds by addition of NH3 molecules (3) base reactions" in which the transition metal is reduced to a carbonyl metalate with complementary oxidation of a CO ligand to CO(NH2)2 (4) valence disproportionations with... 

The properties of the elements of the sixth period are influenced by lanthanide contraction a gradual decrease of the atomic radius with increasing atomic number from La to Lu. The elements of groups 5 to 11 for the fifth and sixth periods have comparable stmctural parameters. For instance, Nb and Ta, as well as the pair Mo and W, have very similar ionic radii, when they have the same oxidation number. As a result, it is very difficult to separate Nb and Ta, and it is also not easy to separate Mo and W. Similarly, Ag and Au have nearly the same atomic radius, 144 pm. Recent studies of the coordination compounds of Ag(I) and Au(I) indicate that the covalent radius of Au is even shorter than that of Ag by about 8 pm. In elementary textbooks the phenomenon of lanthanide contraction is attributed to incomplete shielding of the nucleus by the diffuse 4f inner subshell. Recent theoretical calculations conclude that lanthanide contraction is the result of both the shielding effect of the 4f electrons and relativistic effects, with the latter making about 30% contribution. 

An oxidation-reduction reaction has to be accompanied by a change in the oxidation state of the reactants. Sometimes, these changes aren t that obvious. It helps if you learn how to follow the oxidation states of an element during a chemical reaction. In ionic compounds, it is very obvious where the electrons have been transferred. However, in molecular compounds, electrons are being shared. Oxidation numbers are really fictitious creations that help us better understand atomic behavior. If you remember back to Chapter 6 when we discussed covalent bonds, you may recall that electrons are being shared between atoms in a covalent bond. In many cases, one atom is more electronegative than the other, resulting in a polar... 

The covalent radii of transition elements are subject to two additional effects that influence the values of ionic radii also. A large covalent radius for a given atom is favored by both a low oxidation number and a high coordination number. These two effects are independent neither of each other nor of bond order effects however, an adequate unified treatment of the interrelationships between bond number, coordination number, oxidation number, and bond distances for compounds of the transition metals is best postponed to a more advanced text. 

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