Organometallic fragments coordinated to a multiisocyanide ligand and their physical properties

Preparation of a triisocyanide ligand, 1,3,5-tris[(4-isocyano-3,5-diisoproyl-phenyl)ethynyl]benzene (5), is presented. Ligand 5 is obtained in three steps in 76% overall yield. Reaction of 5 with (eta(5)-Cp*)Rh(Cab(s,s'))(Cab(s,s')= 1,2-S2C2B10H10-S,S') produced the rhodadithiolene adduct [{(eta(5)-Cp*)Rh(Cab(s,s'))((CNC6H2Pr2)-Pr-i-2,6-CC-3)}(3)C6H3-1,3,5] (6). Ligand 5 reacts with Cr(CO)(5)(THF) to give the triisocyanide complex [{Cr(CO)(5)((CNC6H2Pr2)-Pr-i-2,6-CC-3)}(3)C6H3-1,3,5] (8) and with [AuCl(SMe2)] to give the triisocyanide complex [{AuCl((CNC6H2Pr2)-Pr-i-2,6-CC-3)}(3)C6H3-1,3,5] (9). As revealed by a single-crystal X-ray diffraction study, the C(9)-N(3)-C(61) angle of 5.9 degrees of trichromium complex 8 occurs in the plane of the bridge and the gold center has a slightly bent linear configuration with a Cl(1)-Au(1)-C(21) angle of 175.4(4)degrees. The rhenation and platination of 5 employing [Re(bpy)(CO)(3)(AN)]PF6 (AN= acetonitrile) and [((CNN)-N-boolean AND-N-boolean AND)PtCl] (((HCNN)-N-boolean AND-N-boolean AND)= 6-phenyl-2,2'-bipyridine) yielded the luminescent Re(I) and Pt(II) complexes. Full characterization includes structural study of complexes 2, 8, and 9.