UNPRECEDENTED N-E BOND-CLEAVAGE (E = SN, PB) BY R4N- FORMATION, ARCHITECTURE, AND MULTINUCLEAR MAGNETIC-RESONANCE SPECTROSCOPY OF NOVEL SUPRAMOLECULAR [(R4N)(ME3E)(2)M(CN)(6)CENTER-DOT-H2O] ASSEMBLIES (M = FE,CO)( IONS (R = NBU, NPR) )

Novel supramolecular assemblies 2 of the composition [(nBu(4)N)(Me3E)( 2)M(CN)(6) . H2O] (E=Sn, Pb; M=Fe, Co) have been obtained both by spon taneous self-assembly of small ions and by exchange remodeling of the known, sparingly soluble, coordination polymers [(Me3E)(3)M(CN)(6)]. P roduct 2a (E=Sn, M=Fe) was characterized by single-crystal X-ray cryst allography, and its diamagnetic homologue 2b (E=Sn, M=Co) by in-depth multinuclear (C-13, N-15, Co-59, Sn-119) solid-state magnetic resonanc e spectroscopy. The architecture of 2a is based on slightly puckered, porous nets involving coordinative N-cyanide-->Sn and O-water-->Sn bon ds. These nets are stacked regularly and are held together by O-H ... N and (nBu)alpha-C-H ... N hydrogen bonds. This produces nanometer-siz ed channels that host two thirds of the nBu(4)N(+) ions. Unexpected [( Me3Sn(OH2)(2)](+) ions and the remaining third of the nBu(4)N(+) ions are trapped between adjacent [-Fe-CN-Sn-NC-](infinity) chains. Both th e methods of formation of 2a/b and their (probably analogous) structur es are suggestive of a pronounced superiority of concerted O-->Sn and D-H ... N bonding (D=OH and CH2) over an exclusive N-->Sn coordination .