Learn · Organic Chemistry

Curved Arrows for Reactions

The visual language of mechanisms: how a double-barbed arrow tracks an electron pair from an electron-rich source to an electron-poor sink.

Quick answer A curved arrow shows the movement of one electron pair. It always starts at an electron source — a lone pair or a bond — and points to an electron sink, an electron-poor atom or a bond that breaks. Electrons flow from electron-rich (nucleophile) to electron-poor (electrophile), and every arrow must conserve charge and keep second-row atoms at or below an octet.
A mechanism in one line: hydroxide's lone pair attacks the carbon of bromoethane while the C–Br bond breaks, giving ethanol. Two curved arrows tell this whole story.

Curved arrows are how organic chemists write down what the electrons do during a reaction. Structures show where atoms are; arrows show how bonding electrons move to get from reactants to products. Learn to draw them correctly and every mechanism — substitution, addition, elimination, acid–base — becomes the same short vocabulary applied over and over.

1. A curved arrow moves one pair of electrons

The standard curved arrow has two barbs (a full arrowhead) and represents the movement of one electron pair. A single-barbed “fishhook” arrow moves just one electron and is reserved for radical chemistry. Almost every polar mechanism you draw in a first-year course uses only the double-barbed kind.

Nu C δ+ δ− source
The arrow tail sits on the source (a lone pair, here on a negative nucleophile) and the head points at the sink (the electron-poor δ+ carbon). Electrons flow tail→head.

2. The tail starts at electrons, the head shows their destination

Every arrow answers two questions: where do these electrons come from and where do they go. The tail must start on an actual electron source — a lone pair or the middle of an existing bond. It never starts on an atom nucleus or on a positive charge. The head points to where the new electron pair ends up: onto an atom (as a new lone pair) or into the space between two atoms (as a new bond).

Proton transfer: a lone pair on hydroxide reaches out to a proton, forming a new O–H bond and giving water. One arrow, from lone pair to H.

3. Bonds form and break, and charge is conserved

When an arrow points to an atom or between two atoms, a bond forms; when an arrow starts on a bond and points away, that bond breaks. Bookkeeping is automatic if you obey two conservation laws. First, conserve charge: the total charge on the left must equal the total on the right. An atom that donates a lone pair to make a bond becomes one unit more positive; an atom that receives a breaking bond as a lone pair becomes one unit more negative. Second, never exceed an octet on a second-row atom (C, N, O, F). If a new bond would give carbon five bonds, an old bond must break in the same step.

Bond breaking alone: the C–Br bond electrons leave with bromine, so the arrow starts on the bond and ends on Br. Carbon loses a bonding pair and becomes a carbocation — charge is conserved.

4. Nucleophilic attack is a lone pair forming a bond

The first canonical move: a lone pair on an electron-rich atom swings out to form a new bond to an electron-poor atom. This is the arrow you draw for any nucleophile attacking any electrophile. In an SN2 reaction the two arrows happen at once — the nucleophile forms its bond to carbon while the leaving-group bond breaks, so carbon never exceeds an octet.

SN2: cyanide's lone pair attacks carbon (arrow 1, lone pair → new C–C bond) as the C–Br bond breaks toward bromide (arrow 2, bond → lone pair). Two coordinated arrows, one concerted step.

5. A bond can become a lone pair, or become another bond

The remaining two moves round out the toolkit. A bond becoming a lone pair is how a leaving group departs (see the carbocation figure above). A bond becoming a new bond is what happens at a π system: the electrons of a double bond can shift to grab a proton or attack an electrophile. Watch this in nucleophilic addition to a carbonyl — a nucleophile attacks the carbon and the C=O π electrons fold up onto oxygen as a new lone pair.

Carbonyl addition: hydroxide's lone pair attacks the δ+ carbonyl carbon (arrow 1) while the C=O π bond breaks onto oxygen (arrow 2), producing an alkoxide. The π bond became a lone pair.

6. Electrons always flow electron-rich to electron-poor

Every correct arrow in a polar mechanism points the same direction in energy: from a region of high electron density to a region of low electron density. Partial charges (δ+ / δ−) and formal charges are your map. Draw the arrow starting where electrons are abundant — a negative charge, a lone pair, a π bond, an electron-rich atom — and ending where they are wanted, at a δ+ carbon, a proton, or a positive center. If you ever find yourself drawing an arrow that pushes electrons toward a negative charge or onto an already-full octet, the arrow is wrong.

Acid–base as electron flow: ammonia's lone pair (electron-rich) grabs the acetic acid proton, and the O–H bond breaks onto oxygen (electron-poor loses its H), leaving acetate.

7. Summary

A curved arrow is a promise about electrons: two barbs move one pair, the tail sits on a real source (lone pair or bond), and the head shows the pair's destination (a new bond or a new lone pair). Obey the conservation laws — charge in equals charge out, and no second-row atom exceeds an octet — and every step decomposes into three canonical moves: a lone pair forming a bond, a bond becoming a lone pair, and a bond becoming a new bond. Above all, electrons flow from electron-rich to electron-poor. Master this and you can read, check, and write any polar mechanism.

Quiz yourself

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A double-barbed (full arrowhead) arrow shows the movement of one electron pair and is used for polar mechanisms. A single-barbed “fishhook” arrow moves just one electron and is used for radical reactions.

The tail must start on an electron source — a lone pair or the middle of an existing bond. It can never start on an atom nucleus, on a positive charge, or on empty space.

If cyanide only formed a new bond to carbon without the C–Br bond breaking, carbon would have five bonds and exceed its octet. The second arrow — C–Br breaking onto bromide — keeps carbon at an octet, so both happen in one concerted step.

Always from electron-rich to electron-poor. Use formal and partial charges as a map: arrows start at negative charges, lone pairs, and π bonds, and point toward δ+ carbons, protons, and positive centers.

Draw this on the whiteboard

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