PREPARATION AND CHARACTERIZATION OF (C5ME5)RH(CNR)2 AND [(C5ME5)RH(CNR)]2 COMPLEXES

Several complexes of the type (C5Me5)M(CNR)X2have been prepared, where M = Rh and Ir, X = Cl, Br, and I and R = Me, t-Bu, neo-Pn, i-Pr, 2,6-xylyl, and CH2-adamantyl. Two members of this series have been structurally characterized. (C5Me5)Rh(CNMe)Cl2crystallizes in the monoclinic space group P21/n with a = 13.189 (4) Å, b = 8.442 (2) Å, c = 13.473 (6)Å, β = 111.31 (6)°, V= 1398 (2) Å3, and Z = 4. (C5Me5)Ir(CN-2,6-xylyl)I2crystallizes in the monoclinic space group P21/c with a = 11.364 (3) Å, b = 8.436 (3) Å, c = 22.015 (9) Å, β = 97.33 (3)°, V = 2093 (2) Å3, and Z = 4. Reduction of the dihalide derivatives in the presence of isocyanide provides a general route to the bis-substituted products (C5Me5)Rh(CNR)2(R = Me, t-Bu, neo-Pn, i-Pr. 2,6-xylyl, CH2-adamantyl). Reduction of the dihalide complexes in the absence of added isocyanide gives the dimers [(C5Me5)Rh(μ-CNR)]2, one of which has been characterized by X-ray crystallography (R = 2,6-xylyl). The molecule was found to crystallize in the monoclinic space group P21/a with a = 11.165 (6) Å, b = 13.222 (5) Å, c = 11.228 (8) Å, β = 98.43 (5)°, V = 1639.6 (2.9) Å3, and Z = 4. © 1990, American Chemical Society. All rights reserved.