Polymeric silver(I) cyanoacetate contains the classical bis(carboxylato- O, O′) bridged metal dimer arrays in which each pair of adjacent metal atoms is doubly bridged by co-planar carboxylate groups in the syn-syn conformation. These dimeric units are extended into a polymeric chain by terminal linkage of all cyano-nitrogen atoms to silver atoms of adjacent dimer units. In this manner, an individual cyanoacetate anion is O, O′, N-bonded to three different silver centres. EHMO calculations suggest weak direct metal-metal interactions can result from the mixing of metal s and p orbitals into the d 10 shells. Reactions of silver(I) or sodium cyanoacetates with [(η-C 5H 5) 2TiCl 2] afford the bis(cyanoacetato) complex [(η-C 5H 5) 2Ti(O 2CCH 2CN) 2] which has a solid state structure involving O-unidentate carboxylate groups, the cyano-nitrogen atoms not being bonded to a metal. This compound can also be prepared from [(η-C 5H 5) 2Ti(CH 3) 2] and cyanoacetic acid.