Metathesis reactions of the super-Prussian blue systems [(Me3Sn)(3)M(CN)(6)] (M = Co, Ir) with, inter alia, tetrapropylammonium (and -phosphonium) ions: Crystal structures of [(nPr(4)P)(Me3Sn)(2)Co(CN)(6)center dot 2H(2)O] and [(nPr(4)N)(Me3Sn)(2)Ir(CN)(6)center dot 2H(2)O]

Tetrapropylammonium and -phosphonium ions, nPr(4)E(+), react readily with t he polymeric super-Prussian blue derivatives [(Me3Sn)(3)M(CN)(6)] (M = Co, Ir), which are built up of infinite [-M-CN-Sn-NC-] chains, affording the di morphic supramolecular assembly [(nPr(4)E)(Me3Sn)(2)M(CN)(6) . 2H(2)O]. All representatives of the latter type are devoid of any extended [-M-CN-Sn-NC -] backbones. The single-crystal X-ray structures of la-P (E = P; M = Co) a nd 3a (E = N; M = Ir) document new examples of either modification. While M e4N+ and Et4N+ ions do not form sufficiently insoluble, R4N+-containing ass emblies, nBu(4)N(+) and nPen(4)N(+) give rise to similar (i.e., R4N:Me3Sn = 1:2) products as nPr(4)N(+). The slightly modified super-Prussian blue sys tem [{Me2Sn(CH2)(3)SnMe2}(1.5)Co(CN)(6)], 4, reacts with nPr(4)NBr to yield the assembly [(nPr(4)N){Me2Sn(CH2)(3)SnMe2}Co(CN)(6) . 2H(2)O], 4a, the po wder XRD and solid-state NMR spectra of which strongly resemble those of 3a (with two cis-oriented CNSn(Me-3)OH2 ligands). In the absence of suitable single crystals, in particular in the case M = Ir, powder XRD- and multinuc lear solid-state NMR results have been carefully examined in view of specif ic similarities with already established structural patterns. The unexpecte d dimorphism of la, which has been described most recently for M = Co, coul d now also be confirmed for M = Ir, The experimental results of the present study in total indicate that the superiority of coordinative N --> Sn bond s over O --> Sn bonds, in combination with O-H . . . N equivalent to C hydr ogen bridges, decreases, in the presence of R4E+ ions, stepwise with the si ze of R (i.e., from methyl to n-propyl) and of M (i.e., Co vs Ir). (C) 2001 Academic Press.