TY - JOUR
T1 - Manganese(i) templates for the construction of benzannulated triphosphamacrocycles
AU - Edwards, P.G.
AU - Mahon, M.F.
AU - Newman, P.D.
AU - Reixach, E.
AU - Zhang, W.
PY - 2014/11/7
Y1 - 2014/11/7
N2 - 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, 5, 6 and 8.
AB - 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, 5, 6 and 8.
UR - http://www.scopus.com/inward/record.url?scp=84907626301&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1039/c4dt02203c
U2 - 10.1039/c4dt02203c
DO - 10.1039/c4dt02203c
M3 - Article
AN - SCOPUS:84907626301
SN - 1477-9226
VL - 43
SP - 15646
EP - 15655
JO - Dalton Transactions
JF - Dalton Transactions
IS - 41
ER -