Manganese(i) templates for the construction of benzannulated triphosphamacrocycles

P.G. Edwards, M.F. Mahon, P.D. Newman, E. Reixach, W. Zhang

Research output: Contribution to journalArticlepeer-review

6 Citations (SciVal)


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,PhF2)]+, 3. A second precursor, namely fac-[(CO)3Mn(1,2-bpb){P(PhF)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-[(CO3)Mn{H2PC6H4P(H)C6H4P(PhF)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,PhF)]+, 7, which is converted in situ to the more stable dimethylated fac-[Mn(CO3)(tribenzo-9aneP3-Me2,PhF)], 8. The new complexes have been fully characterised by spectroscopic and analytical methods including single crystal X-ray structure determinations for 1, 3, 56 and 8.

Original languageEnglish
Pages (from-to)15646-15655
Number of pages10
JournalDalton Transactions
Issue number41
Early online date26 Aug 2014
Publication statusPublished - 7 Nov 2014


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