Adducts of Cyclotriphosphorus Complexes with Cyclopentadienyl Ruthenium Fragments: Synthesis, Solid‐State Structure and Solution Behaviour

Treatment of the cyclo‐P 3 complexes [(triphos)M(η 3 ‐P 3 )]‐[triphos = 1,1,1‐tris(diphenylphosphanylmethyl)ethane; M = Co ( 1 ), Rh ( 2 )] with stoichiometric amounts of [CpRu‐(CH 3 CN) 2 (PR 3 )]PF 6 [R = Ph ( 3 ), Me ( 4 ), Cy ( 5 )] in CH 2 Cl 2 in the presence of CH 3 CN yields the bimetallic adducts [{(triphos)M}(μ,η 3:1 ‐P 3 ){CpRu(CH 3 CN)(PR 3 )}]PF 6 [M = Co; R = Ph ( 6 ), Me ( 7 ), Cy ( 8 ); M = Rh; R = Ph, ( 9 ), Me ( 10 ), Cy ( 11 )]. The rhodium derivatives 9 and 11 , upon treatment with one equivalent of PMe 3 , form the complexes [{(triphos)Rh}(μ,η 3:1 ‐P 3 ){CpRu(PMe 3 )(PR 3 }]PF 6 [R = Ph ( 12 ), Cy ( 13 )]. On standing in CH 2 Cl 2 , the rhodium complexes 9 and 10 lose acetonitrile to yield compounds with the formula [{(triphos)Rh}(μ,η 3:1,1 '‐P 3 ){CpRu(PR 3 )}]PF 6 [R = Ph ( 14 ), Me ( 15 )]. All the compounds have been characterised by elemental analyses and, in solution, by 31 P and 1 H NMR spectroscopy. The 31 P{ 1 H} EXSY NMR spectroscopic data at different temperatures of 11 and 14 have highlighted the occurrence of independent dynamic processes that exchange both the triphos and the cyclo‐P 3 phosphorus nuclei. An X‐ray structural investigation carried out on 6 has confirmed the occurrence of the μ,η 3:1 ‐ligating behaviour of the cyclo‐P 3 ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)