TRANSITION METAL-CARBON BONDS .44. ORGANO-TRANSITION METAL-COMPLEXES CONTAINING CROWN ETHER GROUPS

Some benzo-crown ethers, substituted in the arene ring, are described e.g. 15-X substituted benzo-15-crown-5 ether(1,X = CCPh, CHCHCOOH, CHCHCOOMe, CHCHCOOEt, CHCHCOCl). 15-Iodo-benzo-15-crown-5 and 18-iodo-benzo-18-crown-6, oxidatively add to Pd(PPh3)4 to give trans-[PdIR(PPh3)2], R=(2) or(3)). [Pt(stilbene)(PPh3)2] reacts similarly with the aryl iodides to give trans-[PtIR(PPh3)2](R=(2), (3), (4)-dimethoxy-phenyl. The platinum complexes with R = (2), (3) or (4) appear to form adducts with sodium iodide in solution. trans-[PtIR(PPh3)2] was converted to the corresponding thiocyanate and chloride (via the nitrate). PhCCR (R = (2) or 3,4-dimethoxyphenyl) react with cis-[PtCl2(PPh3)2 in the presence of hydrazine to give [Pt(PhCCR)(PPh3)2] and PhCCR react with [CO2(CO)8] to give [Co2(PhCCR))CO)6], with Ni(C5H5)2 to give [Ni2(C5H5)2(PhCCR)] and with W(CO)6 in acetonitrile to give [W(CO)(PhCCR)3]; PMe2Ph displaces the CO from [W(CO)(PhCCR)3] to give [W(PMe2Ph)(PhCCR)3]. [Cr(CO)6] reacts with the benzo-crown ethers RH, R = (2),(3) or (4) or with 1,2-dimethoxybenzene to give yellow arenechromium tricarbonyl complexes of the type [Cr(CO)3(RH)]. [Cr(CO)3(benzo-15-crown-5) forms a green 1 1 adduct with NaSCN. © 1979.