Manganese(I) templates for the construction of benzannulated triphosphamacrocycles.

Nine-membered 1,4,7-triphosphamacrocycles with unsaturated benzo-backbones have been prepared using the [(CO)3Mn](+) unit as a template. Two synthetic methods have been employed for the macrocyclisation both of which involve the attack of a coordinated phosphide at an activated, electrophilic ortho-fluorophenyl substituent on a neighbouring pnictide donor. Addition of base to the precursor complex fac-[(CO)3Mn(dfppb)(PhPH2)](+), 1, where dfppb = 1,2-bis[di(2-fluorophenyl)phosphino]benzene, results in the direct formation of the macrocyclic compound fac-[Mn(CO)3(tribenzo-9aneP3-Ph,Ph(F)2)](+), 3. A second precursor, namely fac-[(CO)3Mn(1,2-bpb){P(Ph(F))3}](+), 5, where 1,2-bpb = 1,2-bis(phosphino)benzene, undergoes spontaneous partial macrocyclisation when dissolved in THF to give the intermediate complex fac-[(CO)3Mn{H2PC6H4P(H)C6H4P(Ph(F))2}](+), 6, which contains a linear tridentate phosphine with the unusual combination of a primary, secondary and tertiary phosphine donor. Addition of base to 6 gives the desired macrocyclic complex fac-[Mn(CO)3(tribenzo-9aneP3-H2,Ph(F))](+), 7, which is converted in situ to the more stable dimethylated fac-[Mn(CO)3(tribenzo-9aneP3-Me2,Ph(F))](+), 8. The new complexes have been fully characterised by spectroscopic and analytical methods including single crystal X-ray structure determinations for 1, 3, 5, 6 and 8.