The d-Block Transition Metals

stability of oxidation states across and down the block

A transition metal may be capable of several oxidation states, but in any real situation one of them is usually the stable one — the form you actually find sitting in a bottle or a solution. Iron loves +2 and +3; manganese in water is happiest as +2; chromium prefers +3; permanganate's +7 manganese is a fierce oxidizer just itching to drop down. Which state is stable, and how that changes as you move across a row or down a group, is what lets a chemist predict whether a compound will last or fall apart.

Two simple ideas organize most of it. First, what stabilizes a high oxidation state versus a low one. Very high states (where the metal has given up many electrons and become strongly electron-hungry) are stabilized by small, hard, electron-rich partners that can give density back — above all oxide (O2-) and fluoride (F-). That is why manganese reaches +7 only as the oxide MnO4-, and the highest fluorides exist where high oxides do. Low and even unusual low states (where the metal holds extra electrons) are stabilized by soft pi-acceptor ligands like carbon monoxide, which siphon excess electron density off the metal through back-bonding — this is how we make compounds with the metal in oxidation state zero, such as Ni(CO)4. Second, the trend across the row: early metals reach and keep high states fairly easily (titanium is happy as +4, vanadium as +5), but by the middle the highest states become powerful oxidizers (chromate, dichromate, permanganate), and in the late metals (cobalt, nickel, copper) the +2 state dominates because higher states are too hard to reach.

Down a group the story flips toward higher states: the heavier 4d and 5d congeners hold their high oxidation states far more comfortably than the first-row metal above them. Chromium(VI) is a strong oxidant, but tungsten(VI) in WO3 is placid and ordinary; manganese(VII) is explosive in the wrong company, yet rhenium(VII) oxide is stable and unremarkable. Diagrams such as the Latimer, Frost and Pourbaix plots turn all these tendencies into a quantitative picture, letting you read off which state survives at a given pH and potential — and they reveal when a state will disproportionate, splitting into a higher and a lower state at once.

Compare chromium and tungsten, both group-6 metals. Chromium(VI) as dichromate (Cr2O7 2-) is a strong oxidizer that readily drops to green chromium(III). Tungsten(VI) as WO3 is a stable, dull yellow solid with no urge to be reduced. The high state grows calmer as you go down the group — the same trend that makes the heavier metals favor higher oxidation states.

High states are stabilized by oxide and fluoride, and grow calmer down a group: aggressive Cr(VI) versus placid W(VI).

Stable does not mean inert: a thermodynamically stable oxidation state can still react quickly, and a high state can be perfectly stable until it meets something to oxidize. The diagrams predict which state should win at equilibrium, not how fast it gets there.

Also called
oxidation state stability trends氧化态稳定性趋势氧化態穩定性趨勢