Reaction of the tridentate ligands HCpy 3 or Ppy 3 (py=2-pyridyl) with Cl(CO) 2 py 2 MCPh (M=Mo, W) in THF at elevated temperature followed by metathesis with NaBPh 4 in CH 3 CN affords [(η 3 -Xpy 3 )(CO) 2 MCPh] + (M=W, X=P (2), HC (3); M=Mo, X=P (4)) in high yield. Interaction between 1,1,1-tris(diphenylphosphinomethyl)ethane (CH 3 C(CH 2 PPh 2 ) 3 ) or 1,4,7-trithiacyclononane (TTCN) and Cl(CO) 2 py 2 WCPh in the presence of AgPF 6 in refluxing CH 3 CN gives [{CH 3 C(CH 2 PPh 2 ) 3 }(CO) 2 WCPh]PF 6 (5) and [(TTCN)(CO) 2 WCPh]PF 6 (6), respectively. These complexes exhibit intense absorption bands at 320–340 nm and weak absorptions in the 400–500 nm region, while excitation at 330 nm in dichloromethane give intense orange to red emission. The structure of the product (1) from reaction of Ppy 3 with Cl(CO) 2 py 2 WCPh was established by X-ray crystallography and shows that only two of the pyridine rings in Ppy 3 are bound to the metal center. The crystal structures of 2·EtOH and 3·EtOH show that the W–N distance trans to the carbyne moiety is significantly longer than those which are cis, and this is attributed to the strong trans influence of CPh compared to CO.