Abstract
The synthesis and structural characterization of two families of low-valent vanadium(III) {V6P4} and vanadium(III/IV) {V13P8} phosphonate complexes are reported. Magnetic characterization is reported for representative examples.
Highlights
High-valent vanadium(IV/V)phosphates are an important sub-class of polyoxovanadates with a rich structural chemistry [1]
[VIII6(μ3-O)2(tBuPO3)2(tBuPO3H)2(tBuCO2)8(thf)2] (2) is formed. 2 is centrosymmetric with two oxocentred vanadium triangles linked via four phosphonates (Figure 1)
Our previous work in this area, it is becoming apparent that V(III) chemistry with phosphonates has a good deal in common with Fe(III) chemistry [12]—the major difference being the high air-sensitivity of the vanadium(III) oxidation state
Summary
High-valent vanadium(IV/V) (organo)phosphates are an important sub-class of polyoxovanadates with a rich structural chemistry [1]. The chemistry of molecular examples is dominated by sphere- or bowl-like clusters that display rich host-guest chemistry [2,3,4]. Phosphonates are much rarer and tend to be extended lattice systems [1,5,6]. Molecular low-valent systems – the vanadium(III/IV) form of the organophosphate-templated polyoxovanadates—are rarer still; until recently Zubieta’s (Ph4P)(Bu4N)[(VIVO)6VIII{BuP(O)2OPO3}6] was the sole example [7]. We recently reported straightforward synthetic routes to several new low-valent compounds, including. {V4P4}, {V5P6}, {V6P4}, {V8P8}, {V8P16}, {V9P3} and {V13P8} examples [8,9]. In this work we expand on two of these families – {V6P4} and {V13P8} – to illustrate the generality of this approach
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