Amalgamating metalloligands with coordination networks.
The O(4)-cavity in [Cu{(R,R)-}] ((R,R)-H(2) = 1,6-bis(3-ethoxy-2-hydroxyphenyl)-(3R,4R)-(-)-cyclohexane-1,2-diyl-2,5-diazahexa-1,5-diene) binds HgBr(2) to give P- and M-[Cu{(R,R)-}HgBr(2)]. In the solid state, there is no diastereoselectivity with respect to the handedness of the helical twist adopted by the coordinated Schiff base ligand and [Cu{(R,R)-}HgBr(2)] crystallizes with two independent molecules possessing M- and P-chirality, respectively, in the asymmetric unit. Single crystal structural data confirm that the same phenomenon is observed when [Ni{(R,R)-}] is treated with HgBr(2)or Hg(CN)(2). However, when an excess of Hg(NO(3))(2).H(2)O reacts with [Cu{(R,R)-}], C-mercuration occurs in both 3-ethoxy-2-hydroxyphenyl rings in addition to the coordination of a Hg(NO(3))(2) unit within the O(4)-cavity of [Cu{(R,R)-}]. This results in the formation of a two-dimensional coordination polymer network. The direct C-mercuration of a coordinated Schiff base ligand is not unique to the ligand in [Cu{(R,R)-}], but also occurs during the reaction of [Cu(3)] (H(2) = 1,7-bis(3-ethoxy-2-hydroxyphenyl)- 2,6-diazahepta-1,6-diene) with Hg(NO(3))(2).H(2)O proceeds in an analogous manner with C-mercuration occurs para to the phenolic oxygen atom.
Constable
Edwin C
EC
Department of Chemistry, University of Basel, Spitalstrassse 51, CH-4056, Basel, Switzerland. edwin.constable@unibas.ch
Zhang
Guoqi
G
Housecroft
Catherine E
CE
Zampese
Jennifer A
JA