The 1,8-naphthyridine - functionalized N-heterocyclic carbene 1-benzyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)im;dazol-2-ylidene (BIN) has been successfully coordinated to Pd(II), W(O), Rh(I), and Ir(III), exhibiting its diverse binding modes. Reaction of BIN · HBr with Ag2O, followed by transmetalation with PdCl2(COD)2 provides a cis complex PdCl2(κC2-BIN)2 (1). Treatment of BIN·HBr with W(CO)4(piperidine)2 in acetonitrile affords a chelate complex W(CO)4(κ 2C2,N1′-BIN) (2). Reaction of {RhCI(COD)}2 with KOtBu and subsequent treatment with BIN • HBr in 1:2 and 1:1 ratio results In the mono and dinuclear complexes [Rh(COD)Br(κC2-BIN)] (3) and [{Rh(COD)Br}2(κ N8′:κC2-BIN)] (4), respectively. In complex 3, the "Rh(COD)Br" unit is coordinated to the carbene center, whereas an additional "Rh(COD)Br" unit is attached to naphthyridine nitrogen In complex 4 in an anti arrangement. Under Identical reaction condition, a novel Ir(III) complex [Ir(κ2C2,N1′BIN) (κ2C3′,C2-BIN)(H2O)Br] Br (5) has been synthesized. Complex 5 is proved to be catalytically active In hydrogen transfer reaction from IPrOH. All complexes have been characterized by spectroscopic methods and X-ray crystallography. © 2009 American Chemical Society.