2009
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Abstract: Reactions between the [M(III)(CN)(6)](3-) (M = Fe and Co) anions and the mononuclear complex [Co(II)(dppe)(2)(H(2)O)][BF(4)](2) result in the formation of two isostructural trinuclear clusters {[Co(II)(dppe)(2)](2)[M(III)(CN)(6)]}(BF(4)). Surprisingly, reactions of [Co(dppe)(2)(H(2)O)](BF(4))(2) and [Co(triphos)(CH(3)CN)(2)](BF(4))(2) with [Cr(CN)(6)](3-) yield the mononuclear complexes [Co(dppe)(2)(CN)](BF(4)) and [Co(triphos)(CN)(2)], respectively. In the former case, an unusual pentanuclear intermediate com… Show more

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“…The unequal hexacyanometalate ratio appears to be related to the relatively high solubility of the hexacyanochromate product, reducing its incorporation. The unusual behavior of [Cr­(CN) 6 ] 3– with some Lewis acids has been noted previously, where linkage isomerism, perhaps facilitated by redox processes, leads to enhanced lability of the hexacyanochromate ions …”
Section: Discussionsupporting
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“…The unequal hexacyanometalate ratio appears to be related to the relatively high solubility of the hexacyanochromate product, reducing its incorporation. The unusual behavior of [Cr­(CN) 6 ] 3– with some Lewis acids has been noted previously, where linkage isomerism, perhaps facilitated by redox processes, leads to enhanced lability of the hexacyanochromate ions …”
Section: Discussionsupporting
“…The unusual behavior of [Cr(CN) 6 ] 3− with some Lewis acids has been noted previously, where linkage isomerism, perhaps facilitated by redox processes, leads to enhanced lability of the hexacyanochromate ions. 46 ■ CONCLUSION Mixed-composition Prussian blue analogue particles with controlled concentration gradients have been prepared, and the synthetic conditions and component characteristics that lead to uniform gradients have been elucidated. The successful quenching of the kinetic gradient products primarily depends on the relative precipitation rates of the individual PBA species.…”
Section: ■ Discussionmentioning
“…To compare the effects of ligand field strength on the electronic structures of cyanometallates, we synthesized the linkage isomer (TBA)3[Cr(NC-BPh3)6] (Cr-III-NC-BPh3) (cyanides are strong σdonors and weak π-acceptors). 39,63 When Cr-III was refluxed with BPh3 in MeCN, a dramatic color change from pale yellow to orange-red occurred. 39 Remarkably, the reaction triggered inversion of all six cyanide ligands, affording a borane-capped hexakiscyanoborate complex (Figure 2(d)).…”
Section: N-methylpyrrolidinonementioning
“…35 Reaction of [Co(dppe) 2 (H 2 O)](BF 4 ) 2 with [Cr(CN) 6 ] 3À yields the mononuclear complex [Co(dppe) 2 (CN)](BF 4 ) via an unusual pentanuclear intermediate which was isolated as {[Co II 3 (dppe) 4 (MeCN)][Cr III (CN) 6 ] 2 }. 36 Solution IR spectroscopy, revealed a gradual conversion of the n(CRN) stretches of the starting materials to those of the CN-bridged intermediate and eventually to the single n(CRN) stretch of the final mononuclear product. The loss of carbon-bound CN ligands from [Cr(CN) 6 ] 3À occurs on a sufficiently slow time-scale for observation of varying degrees of cyanide linkage isomerism in the trigonal bipyramidal complex {[Co(tmphen) 2 ] 3 [Cr(CN) 6 ] 2 }.…”
Section: Isomerizationmentioning