183968-70-9Relevant academic research and scientific papers
Mixed carbonyl-nitrile complexes of dirhenium(II). the structural characterization and reactivity of salts of the [Re2Cl3(μ-dPPm)2(CO)(NCMe)n] + cations (dppm = Ph2PCH2PPh2, n = 1 or 2)
Chantler, James,Fanwick, Phillip E.,Walton, Richard A.
, p. 219 - 228 (2007/10/03)
The monocarbonyl complexes Re2X4(μ-dppm)2(CO) (X = Cl or Br) react with stoichiometric quantities of the nitriles RCN (R = Me or Ph) in the presence of TlY (Y = PF6 or O3SCF3) to afford complexes of the type [Re2X3(μ-dppm)2(CO)(NCR)]Y and [Re2X3(μ-dppm)2(CO)(NCR)2]Y in high yield. Crystal structure determinations on the salts [Re2Cl3(μ-dppm)2(CO)(NCMe)]O 3SCF3 and [Re2Cl3(μ-dppm)2(CO)(NCMe) 2]ReO4 have shown that the former has the unsymmetrical structure [(MeCN)(CO)ClRe(μ-dppm)2ReCl2]+ with a Re≡Re bond (Re-Re distance 2.2881(7) A?), while the bis-nitrile complex is the edge-sharing bioctahedron [(MeCN)ClRe(μ-Cl)(μ-CO)(μ-dppm)2ReCl(NCMe)]+, with an all-cis arrangement of the μ-CO and two MeCN ligands and a Re=Re bond (Re-Re distance 2.5669(4) A?). The species [Re2X3(μ-dppm)2(CO)(NCMe)]+ and [Re2X3(μ-dppm)2(CO)(NCMe)2] + readily interconvert upon the addition or loss of an acetonitrile ligand and, along with their benzonitrile analogues, they react with halide, XylNC and acetylene to afford Re2X4(μ-dppm)2(CO), [Re2X3(μ-dppm)2(CO)(CNXyl)2]Y and [Re2X3(μ-dppm)2(CO)(η2-C 2H2)]Y, respectively.
Reactions of the Dirhenium(II) Complexes Re2X4(μ-dppm)2 (X = Cl, Br; dppm = Ph2PCH2PPh2) with Isocyanides. 11.1 A Triply Bonded Dirhenium Complex Containing a Labile Acetonitrile Ligand. Synthesis, Structural Characterization, and Reactivity
Wu, Wengan,Anand Subramony,Fanwick, Phillip E.,Walton, Richard A.
, p. 6784 - 6788 (2008/10/09)
The reaction of the open bioctahedral form of Re2Cl4(μ-dppm)2(CO)(CNXyl) (1), where XylNC = 2,6-dimethylphenyl isocyanide, with TlO3SCF3 in the presence of acetonitrile proceeds with retention of stereochemistry at the dirhenium unit to afford the complex [Re2Cl3(μ-dppm)2(CO)(CNXyl)(NCCH 3)]O3SCF3 (3). The single-crystal X-ray structure determination of 3 shows that a Re=Re bond is retained (the Re-Re distance is 2.378(3) A?) and that it is the chloride ligand trans to the XylNC ligand of 1 which is labilized. Complex 1 reacts with TlO3SCF3 in a noncoordinating solvent to produce the unsymmetrical complex [Re2Cl3(μ-dppm)2(CO)(CNXyl)]O 3-SCF3 (2), through loss of this same chloride ligand of 1 and CO transfer from the adjacent Re center. The acetonitrile ligand of 3 is very labile and is readily displaced by XylNC and t-BuNC, with retention of stereochemistry, to produce complexes of stoichiometry [Re2Cl3(μ-dppm)2(CO)(CNXyl)(CNR)]O 3SCF3 (R = Xyl, 4a; R = t-Bu, 4b). In a noncoordinating solvent, the nitrile ligand of 3 is lost and 2 is formed following CO transfer; this conversion is reversed upon the reaction of 2 with acetonitrile. When 3 is treated with CO, the acetonitrile ligand is again displaced, but in this instance the reaction is accompanied by a structure change to produce an edge-sharing bioctahedral complex of the type [Re2(μ-CO)(μ-Cl)(μ-dppm)2Cl 2(CO)(CNXyl)O3SCF3 (5).
