[3+2] Cycloadditions of Metallo Nitrile Ylides and Metallo Nitrile Imines with Metal Carbonyl, Thiocarbonyl, and Isocyanide Complexes: Heterodimetallic Systems with Bridging Heterocycles [1]

The reactions of [Re(CO) 6 ] + , [FeCp(CO) 2 CS] + and [FeCp(CNPh) 3 ] + with the metallo nitrile ylides [ M – {C + =N–C – (H)CO 2 Et}(CO) 5 ] – ( M = Cr, W) and the chromio nitrile imine [Cr – {C + =N–N – H}(CO) 5 ] – (generated by mono‐ α ‐deprotonation of the parent isocyanide complexes) to give neutral 5‐metallated 1,3‐oxazolin‐ ( 1 ), 1,3‐thiazolin‐ ( 2 ), imidazolin‐ ( 3 , 4 ), 1,3,4‐oxdiazolin‐ ( 5 ), 1,3,4‐thiadiazolin‐ ( 6 ) and 1,3,4‐triazolin‐2‐ylidene ( 8 ) chromium and tungsten complexes represent the first all‐organometallic versions of Huisgen ’s 1,3‐dipolar cycloadditions. The formation of 6 and 8 is accompanied by partial decomposition to (OC) 5 Cr–C≡N–FeCp L 2 { L = CO ( 7 ), CNPh ( 9 )}. The structures of 4a and 5 have been characterized by X‐ray diffraction.