Synthesis and structural characterisation of a novel 2,3-distibene-1,4-dione complex, [Pt(PEt3)2{η2-ButC(O)SbSbC(O)But}]

Size Matters: Synthesis of Group 13 Metal‐Substituted Dipnictanes by E‐C Bond Homolysis

“…Compounds 9 – 12 belong to the very short list of structurally characterized metal‐substituted dipnictanes. Aside from homoleptic germyl‐ and stannyl‐substituted distibanes [(Me 3 Ge) 2 Sb] 2 [ 37 ] and [(Me 3 Sn) 2 Sb] 2 , [ 38 ] there are only two additional examples: the homoleptic bis iron‐substituted diarsane [CpFe(CO) 2 (Ph)As] 2 [ 39 ] as well as the diarsenide‐dione bridged complex, [Et 3 P(Cl)Pt{ t Bu(O)C}As] 2 , [ 40 ] respectively.…”

Reactions of 2-arsa- and 2-stiba-1,3-dionato lithium complexes with group 4–7 metal halides

“…For example, whereas b-diketonates generally bind to main group and transition metals in variations of the chelating g 2 -O,O-mode, the presence of 2-coordinate pnicogen centres in 1 has led to them exhibiting a variety of ligating modes which include g 2 -O,O-; g 1 -E; g 1 -E:g 1 -O:g 2 -CO; g 1 -E:g 2 -O,O-and l-g 1 :g 1 -E (as in, for example, [2][3][4][5] [6]. In addition, the weakness of the E-C bonds in transition metal complexes of 1 can lead to their cleavage and the formation of novel and previously inaccessible complex types, for example the only known functionalised distibene which is stabilised in the complex, cis-[Pt(PEt 3 ) 2 {g 2 -Sb,Sb-(Bu t )(O)CSb@SbC(O)(Bu t )}] [7].…”

The synthesis and structural characterisation of 2-arsa- and 2-stiba-1,3-dionato complexes of s- and p-block elements

“…The mechanism of formation of 16 is unknown but presumably involves the selenodiacylarsenide, [PhSeAs{C(O)Bu t } 2 ], as an unstable intermediate that undergoes As-C bond cleavage and rearrangement to generate the selenaester, PhSeC(O)-Bu t , which displaces DME of solvation from the lithium arsadionate starting material, 2, to form the observed complex. Arsenic-carbon bond cleavages in diacylarsenido complexes have been observed before 4 and most likely lead to the decomposition observed in the other group 16 based reactions mentioned above.…”

“…The molecular structures of 9-11 are depicted in Figs. 4-6 (see Table 1). Compound 9 is isostructural and isomorphous to 6 and as in that compound the As-C and C-O bond lengths lie between those expected for double and single interactions.…”

“…For example, whereas b-diketonates generally bind transition metals in variations of the chelating Z 2 -O,O mode, the presence of a low coordinate pnictide centre in 1 allows them to coordinate metals in a variety of ways, which include Z 2 -O,O-; Z 1 -E; Z 1 -E:Z 1 -O:Z 2 -CO; Z 1 -E:Z 2 -O,O-and m-Z 1 :Z 1 -E. 2,3 In addition, the weakness of the Sb-C bond of 2-stiba-1,3-dionates has led to their use as precursors to previously inaccessible complex types such as the first example of a functionalised distibene, which is stabilised within the coordination sphere of a transition metal fragment: cis-[Pt(PEt 3 ) 2 {Z 2 -Sb,Sb-C(Bu t )(O)Sb=SbC(O)(Bu t )}]. 4 Despite the coordinative versatility that heterodionates have shown towards transition metals, little work has looked at their interaction with main group elements. Indeed, this can be confined to the preparation of the lithium salts of these ligands, [Li{Z 2 -O,O-OC(R)EC(R)O}], 5,6 which are invariably used as starting materials in the transition metal based studies.…”