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Abbreviations used for diphosphines and related ligands: PPh 2CH2-PPh2 (dppm, cis-PPh 2CHCHPPh2 (dppv, PPh2(CH2) 2PPh2 (dppe, PPh2-(CH2) 3PPh2 (dppp, 1,1′-bis(diphenylphosphino)ferrocene (dppf, S)-2-(dimethylamino)-3-phenylpropyl]diphenylphosphine S-phephos
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2 (dppp), 1,1′-bis(diphenylphosphino)ferrocene (dppf), [(S)-2-(dimethylamino)-3-phenylpropyl]diphenylphosphine (S-phephos).
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6, the coordinated phosphorus resonances are non-first-order and are instead observed as a multiplet between 22.0 and 23.7 ppm; see Figure SI.
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6, the coordinated phosphorus resonances are non-first-order and are instead observed as a multiplet between 22.0 and 23.7 ppm; see Figure SI.
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Considerable shifts to higher frequency are observed for the C 4 resonance (see Scheme 1 for labeling) on substitution of the CH3CN, indicative of weaker coordination of C4 to the metal center due to increased steric bulk in the coordination sphere. The increase in steric bulk is also apparent from changes in the p-cymene H 7 and H8 resonances and the H9 and H 10 resonances, which become distinctly diastereotopic for [2a-e]PF6, particularly for [2b]PF6 and [2e]PF6. In the case of [2e]PF6, the observation of a NOE interaction between H6 and H12 Experimental Section, Figure 6, indicating that the dppf ligand adopts a conformation with the ferrocene moiety approaching the plane of the coordinated arene, may help explain the origin of these shifts
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12 (Experimental Section, Figure 6), indicating that the dppf ligand adopts a conformation with the ferrocene moiety approaching the plane of the coordinated arene, may help explain the origin of these shifts.
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The overall of activation is comprised of both intrinsic and solvational contributions (ΔV‡obs, ΔV‡ intr, ΔV‡solv, Because the chelation of 4a and 4b involves the creation of charged species, 5a, Cl, 5b]+Cl, respectively, the overall of activation value will include a negative contribution from changes in the solvation during this process electrostriction, making the precise interpretation of the overall of activation less straightforward [van Eldik, R, Hubbard, C. D. High Pressure Chemistry; van Eldik, R, Klärner, F.-G, Eds, Wiley-VCH: Weinhein, 2002, However, owing to the similarity of these two complexes, contributions from electrostriction are likely to be similar. In addition to the of activation, similar arguments apply to the interpretation of the activation entropies for the chelation of
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31P{1H} NMR (CH2ClCH2Cl, internal D2O reference, δ 38.8 (t, 2J pp, 34, 1P, PPh3, 5.6 (dd, 2J pp, 69, 2Jpp, 34, 1P, PPh 2, 4.7 (dd, 2Jpp, 69, 2JPP, 34, 1P, P′Ph2, The analogous compounds [RuCl2(PPh3)(η2-(P-P, P-P, dppp, dppb) have been reported and exhibit similar 31P NMR spectra, although with larger J(P-p)(p-P) coupling constants [ref 18
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