Reaction of the bidentate ligand Ph 2 P(o-C 6 H 4 )C(dO)H (abbreviated as PCHO) with W(CO) 3 (η 3 -(MeNCH 2 ) 3 ) at room temperature affords W(CO) 3 (η 1 -PCHO)(η 3 -PCHO) (1), which subsequently loses a carbonyl ligand to give W(CO) 2 (η 3 -PCHO) 2 (2). Further treatment of 2 with PCHO in refluxing benzene results in carboncarbon coupling of the PCHO ligands to produce W(CO)-(η 3 -PCHO)(η 3 -(PCHO) 2 ) (3). The structures of 1-3 have been determined by an X-ray diffraction study. The PCHO ligands in these compounds act as chelating phosphine-aldehydes with the aldehyde groups coordinating in a π fashion.

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