Journal of the Chemical Society, Dalton Transactions p. 2511 - 2518 (1996)
Update date:2022-09-26
Topics:
Bardaji, Manuel
Brown, Nathan C.
Christofides, Aristides
Connelly, Neil G.
The complex [Rh2(CO)4(μ-RN3R)2] 1 reacted with the cyanomanganese ligands cis-[Mn(CN)(CO)2(L-L)] [L-L = Ph2PCH2PPh2 (dppm), L = P(OEt)3 2 or P(OPh)3 3; L-L = Ph2PCH2CH2PPh2 (dppe), L = PEt3 4] in n-hexane under reflux, or with trans-[Mn(CN)(CO)2L(L-L)] [L-L = dppm, L = P(OEt)3 8 or P(OPh)3 9] or [Mn(CN)(NO)L(cp′)] [L = P(OPh)3 12 or PPh3 13, cp′ = η-C5H4Me], in CH2Cl2 in the presence of ONMe3, giving [Rh2{(μ-NC)MnLx}(CO)3(μ-RN 3R)2] {Lx = cis-(CO)2[P(OEt)3](dppm) 5, cis-(CO)2[P(OPh)3](dppm) 6, cis-(CO)2(PEt3)(dppe) 7, trans-(CO)2[P(OEt)3](dppm) 10, trans-(CO)2[P(OPh)3](dppm) 11, (NO)[P(OPh)3](cp′) 14 or (NO)(PPh3)(cp′) 15}. The tricarbonyls underwent one-electron oxidation at a platinum-disc electrode and reacted with [Fe(cp)2][PF6] (cp = η-C5H5) in CH2Cl2 to give the corresponding paramagnetic complexes 5+-7+, 10+, 11+, 14+ and 15+ which contain [Rh2]3+ cores. The addition of compounds 2 or 8 to 5+ or 10+, or of 3 or 9 to 6+ or 11+, resulted in further carbonyl substitution to give the dicarbonyl complexes [Rh2{(μ-NC)MnLx}2(CO) 2(μ-RN3R)2]+ 16+-21+ which reacted with [Fe(cp)2][PF6] in the presence of chloride ion to give the diamagnetic [Rh2]4+-containing cations [Rh2Cl{(μ-NC)MnLx}2(CO) 2(μ-RN3R)2]+ 22+-24+. The ESR spectra of the paramagnetic [Rh2]3+-containing cations, and the effects of varying the cyanomanganese ligand on the order in which the redox-active sites (Rh2 and Mn) of the tri- and tetra-metallic complexes are oxidised, are discussed.
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