A New Route to Heterobimetallic C 3 Complexes via C⋮C Metatheses of 1,3-Diynyl Ligands: Synthesis and Structure of (η 5 -C 5 Me 5 )Re(NO)(PPh 3 )(C⋮CC⋮)W(O- t -Bu) 3
- Award ID(s):
- 9732605
- NSF-PAR ID:
- 10164899
- Date Published:
- Journal Name:
- Organometallics
- Volume:
- 18
- Issue:
- 26
- ISSN:
- 0276-7333
- Page Range / eLocation ID:
- 5438 to 5440
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The reduction potentials (reported vs. Fc + /Fc) for a series of Cp′ 3 Ln complexes (Cp′ = C 5 H 4 SiMe 3 , Ln = lanthanide) were determined via electrochemistry in THF with [ n Bu 4 N][BPh 4 ] as the supporting electrolyte. The Ln( iii )/Ln( ii ) reduction potentials for Ln = Eu, Yb, Sm, and Tm (−1.07 to −2.83 V) follow the expected trend for stability of 4f 7 , 4f 14 , 4f 6 , and 4f 13 Ln( ii ) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4f n 5d 1 Ln( ii ) ions ( n = 2–14), fall in a narrow range of −2.95 V to −3.14 V. Only cathodic events were observed for La and Ce at −3.36 V and −3.43 V, respectively. The reduction potentials of the Ln( ii ) compounds [K(2.2.2-cryptand)][Cp′ 3 Ln] (Ln = Pr, Sm, Eu) match those of the Cp′ 3 Ln complexes. The reduction potentials of nine (C 5 Me 4 H) 3 Ln complexes were also studied and found to be 0.05–0.24 V more negative than those of the Cp′ 3 Ln compounds.more » « less