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Title: The series of carbon-chain complexes {Ru(dppe)Cp*}₂{μ-(C≡C)x} (x = 4–8, 11): Synthesis, structures, properties and some reactions

The construction of a series of compounds {Ru(dppe)Cp*}2(μ-C2x) (Ru*-C2x-Ru*, x = 4–8, 11)) is described. A direct reaction between RuCl(dppe)Cp* and Me3Si(Ctriple bond; length of mdashC)4SiMe3 afforded Ru*-C8-Ru* in 89% yield. The Pd(0)/Cu(I)-catalysed coupling of Ru{Ctriple bond; length of mdashCCtriple bond; length of mdashCAu(PPh3)}(dppe)Cp*Ru*-C4-Au (2 equiv.) with diiodoethyne gave Ru*-C10-Ru* (64%), or of 1 equiv. with I(Ctriple bond; length of mdashC)3I gave Ru*-C14-Ru* (36%); similarly, Ru{(Ctriple bond; length of mdashC)4Au(PPh3)}(dppe)Cp*Ru*-C8-Au and I(Ctriple bond; length of mdashC)3I gave Ru*-C22-Ru* (12%). Desilylation (TBAF) of Ru{(Ctriple bond; length of mdashC)xSiMe3}(dppe)Cp*Ru*-C2x-Si (x = 3, 4) followed by oxidative coupling [Cu(OAc)2/py] gave Ru*-C12-Ru* (82%) and Ru*-C16-Ru* (58%), respectively. Similar oxidative coupling of Ru(Ctriple bond; length of mdashCCtriple bond; length of mdashCH)(dppe)Cp* was a second route to Ru*-C8-Ru* (82%). Appropriate precursors are already known, or obtained by coupling of Ru*-C2x-Si (x = 2, 4) with AuCl(PPh3)/NaOMe [Ru*-C4-Au, 95%; Ru*-C8-Au, 74%] or from Pd(0)/Cu(I) catalysed coupling of Ru*-C2x-Au (x = 2, 3) with I(Ctriple bond; length of mdashC)2SiMe3 (Ru*-C8-Si, 64%; Ru*-C10-Si, 2%). Reactions between Ru*-C2x-Ru* (x = 3, 4) and Fe2(CO)9 gave {Fe3(CO)9}{μ3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}2Fe(C3-Ru*)2 and {Fe3(CO)9}{μ3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}{μ3-C(Ctriple bond; length of mdashC)2[Ru(dppe)Cp*]} Fe(C3-Ru*)(C5-Ru*), respectively. The redox properties of the series of complexesmore » with 2x = 2–16 were measured and showed a diminution of the separation of the first two oxidation potentials, ΔE = E2 - E1, with increasing carbon chain length. The X-ray-determined molecular structures of Ru*-C8-Si, Ru*-C8-Ru*, Ru*-C14-Ru* (two C6H6 solvates), {Ru(PPh3)2Cp}2{μ-(Ctriple bond; length of mdashC)4}·4CHCl3Ru-C8-Ru·4CHCl3 and of Fe(C3-Ru*)2 and Fe(C3-Ru*)(C5-Ru*) are reported.« less
 [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [3] ;  [3]
  1. Univ. of Adelaide, South Australia (Australia)
  2. Univ. of Waikato, Hamilton (New Zealand)
  3. Univ. of Western Australia, Crawley (Western Australia)
Publication Date:
OSTI Identifier:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Polyhedron; Journal Volume: 86; Journal Issue: C
Research Org:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS).
Sponsoring Org:
Country of Publication:
United States
Ruthenium; carbon-chain; X-ray structure; electrochemistry; carbyne