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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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Supplementary files

Article information

21 Jul 2014
23 Aug 2014
First published
26 Aug 2014

Dalton Trans., 2014,43, 15646-15655
Article type
Author version available

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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