Syntheses of cationic tri- and di-carbonyl complexes of manganese(I) with diphosphines from the appropriate neutral bromocarbonyls
- 1 January 1981
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 2049-2053
- https://doi.org/10.1039/dt9810002049
Abstract
Reaction of the complexes fac-[MnBr(CO)3(L–L)][L–L = Ph2P(CH2)nPPh2, n= 1 (dppm) or 2 (dppe)] with phosphorus-donor ligands, L, leads to the complexes cis,cis-[MnBr(CO)2(L–L)L]. These neutral dicarbonyls are oxidized by NO2 or [NO][PF6] to the unstable cationic species trans-[MnBr(CO)2(L–L)L]+ which may be isolated as hexafluorophosphate salts and which lead to the neutral trans-[MnBr(CO)2(L–L)L] when reduced by hydrazine. Replacement of the bromo-ligand in either cis,cis- or trans-[MnBr(CO)2(L–L)L], using TI[PF6] in the presence of another ligand L′(N or P donor), results in the formation of cis,cis- or trans-[Mn(CO)2(L–L)LL′][PF6] respectively, or of mer-[Mn(CO)3(L–L)L][PF6] if L′= CO. However, using Ag[CIO4] as the halogen abstracter, the perchlorate salts of the cis,cis-cationic dicarbonyls (or the mer tricarbonyls) are obtained regardless of the neutral bromocarbonyl isomer used.Keywords
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