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Issue 41, 2014
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Manganese(I) templates for the construction of benzannulated triphosphamacrocycles

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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-[(CO)3Mn{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(CO)3(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, 5, 6 and 8.

Graphical abstract: Manganese(i) templates for the construction of benzannulated triphosphamacrocycles

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The article was received on 21 Jul 2014, accepted on 23 Aug 2014 and first published on 26 Aug 2014

Article type: Paper
DOI: 10.1039/C4DT02203C
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Citation: Dalton Trans., 2014,43, 15646-15655

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    Manganese(I) templates for the construction of benzannulated triphosphamacrocycles

    P. G. Edwards, M. F. Mahon, P. D. Newman, E. Reixach and W. Zhang, Dalton Trans., 2014, 43, 15646
    DOI: 10.1039/C4DT02203C

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