TY - JOUR
T1 - Inert Transition Metal Ion Complexes in Organic Synthesis
T2 - Protection and Activation
AU - Donnelly, Paul S.
AU - Harrowfield, Jack M.
AU - Koutsantonis, George A.
AU - Lengkeek, Nigel A.
AU - Ling, Irene
AU - Nealon, Gareth L.
AU - McInnes, Lachlan E.
AU - Skelton, Brian W.
AU - Sobolev, Alexandre N.
AU - White, Allan H.
AU - White, Jonathan M.
PY - 2023/9/15
Y1 - 2023/9/15
N2 - Single-crystal X-ray diffraction studies for a variety of metal ion complexes of functionalised sarcophagines (sarcophagine=sar=3,6,10,13,16,19-hexa-azabicyclo[6.6.6]icosane) have further confirmed not only that the form of the metal ion/sar unit is unique for each metal, albeit with a sensitivity of the conformation to the associated counter anions, but also that for any given metal and ligand substituent, the dimensions (bond lengths and angles) of the complex and the substituent at the secondary nitrogen centres do not differ significantly from those of the isolated components. Despite this, where the substituent contains reactive sites, the reactivity differs markedly from that of their form in an uncoordinated substrate. Rationalisations are offered for these differences, in part through the use of Hirshfeld surface analysis of the intermolecular interactions. The kinetic inertness of the complexes means that the metal ions can be considered to act as regioselective protecting groups.
AB - Single-crystal X-ray diffraction studies for a variety of metal ion complexes of functionalised sarcophagines (sarcophagine=sar=3,6,10,13,16,19-hexa-azabicyclo[6.6.6]icosane) have further confirmed not only that the form of the metal ion/sar unit is unique for each metal, albeit with a sensitivity of the conformation to the associated counter anions, but also that for any given metal and ligand substituent, the dimensions (bond lengths and angles) of the complex and the substituent at the secondary nitrogen centres do not differ significantly from those of the isolated components. Despite this, where the substituent contains reactive sites, the reactivity differs markedly from that of their form in an uncoordinated substrate. Rationalisations are offered for these differences, in part through the use of Hirshfeld surface analysis of the intermolecular interactions. The kinetic inertness of the complexes means that the metal ions can be considered to act as regioselective protecting groups.
KW - cage amine
KW - complex
KW - hydrogen bonding
KW - metal
KW - sarcophagine
UR - http://www.scopus.com/inward/record.url?scp=85167570071&partnerID=8YFLogxK
U2 - 10.1002/asia.202300556
DO - 10.1002/asia.202300556
M3 - Article
C2 - 37442812
AN - SCOPUS:85167570071
SN - 1861-4728
VL - 18
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 18
M1 - e202300556
ER -