The Heptacyanotungstate(IV) Anion: A New 5 d Transition‐Metal Member of the Rare Heptacyanometallate Family of Anions

Abstract

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A Family of Octahedral Magnetic Molecules Based on [NbIV(CN)8]4–

“…In addition to the plethora of 3d magnetic systems based on cyanide, there are exciting opportunities for the chemistry of 4d and 5d transition metals owing to their rich redox chemistry, expanded coordination spheres, and stronger spin–orbit coupling. − These fascinating possibilities notwithstanding, coordination compounds based on cyanide complexes of early 4d and 5d transition metals are underrepresented due to their elusive character and relatively high oxygen and moisture sensitivity, one such example being octacyanoniobate­(IV). , Several 2-D , and 3-D − coordination polymers based on this anion have been reported, some of which exhibit unique combinations of physical and chemical properties, , but there are only three examples of discrete assemblies involving this “fragile” cyanometalate; there are two molecules with manganese­(II) and one involving nickel­(II) as a second metal center . Attempts have been made to prepare other discrete congeners such as Co II -Nb IV without success …”

The First Homoleptic Complex of Seven-Coordinated Osmium: Synthesis and Crystallographical Evidence of Pentagonal Bipyramidal Polyhedron of Heptacyanoosmate(IV)

“…Moreover, the homoleptic coordination compounds of Os with purely inorganic ligands comprise mainly hexaligated complexes, unlike its nearest neighbor of the 5d row, Re, which demonstrates coordination numbers from six to eight [33][34][35][36]. The recent isolation of heptacyanotungstate(IV) as a salt (n-Bu 4 N) 3 [W IV (CN) 7 ] (n-Bu 4 N = tetra-n-butylammonium) [37] has widened the family of rare heptacyanometallate anions. tetra-n-butylammonium) [37] has widened the family of rare heptacyanometallate anions.…”

“…The recent isolation of heptacyanotungstate(IV) as a salt (n-Bu 4 N) 3 [W IV (CN) 7 ] (n-Bu 4 N = tetra-n-butylammonium) [37] has widened the family of rare heptacyanometallate anions. tetra-n-butylammonium) [37] has widened the family of rare heptacyanometallate anions. Here, we present the pioneering results in osmium coordination chemistry involving the synthesis and exhaustive structural study of the (n-Bu4N)3[Os IV (CN) 7], (1)-the only homoleptic complex with heptacoordinated osmium (Figure 1), which also represents the first example of fully characterized cyanoosmate(IV).…”