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

Pd(0)/Cu(I)-catalysed reactions between iodo- or diiodo-alkynes and (phosphine)gold-substituted alkynyl-ruthenium complexes have given {Ru(dppe)Cp∗}2{ μ -(CC)x} (x=4–8, 11). Their redox properties have been measured, and seven X-ray structures are described. [Display omitted] The construction of a s...

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Bibliographic Details
Published in:Polyhedron 2015-01, Vol.86 (C), p.43-56
Main Authors: Bruce, Michael I., Cole, Marcus L., Ellis, Benjamin G., Gaudio, Maryka, Nicholson, Brian K., Parker, Christian R., Skelton, Brian W., White, Allan H.
Format: Article
Language:English
Subjects:
Carbon-chain
Carbyne
Electrochemistry
Ruthenium
X-ray structure
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Summary:Pd(0)/Cu(I)-catalysed reactions between iodo- or diiodo-alkynes and (phosphine)gold-substituted alkynyl-ruthenium complexes have given {Ru(dppe)Cp∗}2{ μ -(CC)x} (x=4–8, 11). Their redox properties have been measured, and seven X-ray structures are described. [Display omitted] 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(CC)4SiMe3 afforded Ru∗-C8-Ru∗ in 89% yield. The Pd(0)/Cu(I)-catalysed coupling of Ru{CCCCAu(PPh3)}(dppe)Cp∗Ru∗-C4-Au (2equiv.) with diiodoethyne gave Ru∗-C10-Ru∗ (64%), or of 1equiv. with I(CC)3I gave Ru∗-C14-Ru∗ (36%); similarly, Ru{(CC)4Au(PPh3)}(dppe)Cp∗Ru∗-C8-Au and I(CC)3I gave Ru∗-C22-Ru∗ (12%). Desilylation (TBAF) of Ru{(CC)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(CCCCH)(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(CC)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-CCC[Ru(dppe)Cp∗]}2Fe(C3-Ru∗)2 and {Fe3(CO)9}{μ3-CCC[Ru(dppe)Cp∗]}{μ3-C(CC)2[Ru(dppe)Cp∗]} Fe(C3-Ru∗)(C5-Ru∗), respectively. The redox properties of the series of complexes 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-(CC)4}·4CHCl3Ru-C8-Ru·4CHCl3 and of Fe(C3-Ru∗)2 and Fe(C3-Ru∗)(C5-Ru∗) are reported.
ISSN:0277-5387
DOI:10.1016/j.poly.2014.04.052