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[Cp(CO)₂Mo{NR^*[Rh(norbornadiene)]-CH(pyridyl)}], a Rhodium Complex with an Asymmetric Molybdenum Atom in the Chelate Skeleton^†

Corresponding Author

Prof. Dr. Henri Brunner

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)Search for more papers by this author

Dr. Joachim Wachter,

Dr. Joachim Wachter

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)

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Dipl.-Chem. Johann Schmidbauer,

Dipl.-Chem. Johann Schmidbauer

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)

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Prof. George M. Sheldrick,

Prof. George M. Sheldrick

Institut für Anorganische Chemie der Universität, Tammannstr. 4, D-3400 Göttingen (FRG)

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Priv.-Doz. Peter G. Jones,

Priv.-Doz. Peter G. Jones

Institut für Anorganische Chemie der Universität, Tammannstr. 4, D-3400 Göttingen (FRG)

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Prof. Dr. Henri Brunner,

Corresponding Author

Prof. Dr. Henri Brunner

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)Search for more papers by this author

Dr. Joachim Wachter,

Dr. Joachim Wachter

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)

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Dipl.-Chem. Johann Schmidbauer,

Dipl.-Chem. Johann Schmidbauer

Institut für Anorganische Chemie der Universität, Universitätsstr. 31, D-8400 Regensburg (FRG)

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Prof. George M. Sheldrick,

Prof. George M. Sheldrick

Institut für Anorganische Chemie der Universität, Tammannstr. 4, D-3400 Göttingen (FRG)

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Priv.-Doz. Peter G. Jones,

Priv.-Doz. Peter G. Jones

Institut für Anorganische Chemie der Universität, Tammannstr. 4, D-3400 Göttingen (FRG)

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First published: April 1986

https://doi.org/10.1002/anie.198603711

Citations: 7

^†

Optically Active Transition Metal Complexes, Part 90. This work was supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, and BASF AG. Part 89: I. Bernal, G. M. Reisner, H. Brunner, G. Riepl, Inorg. Chim. Acta 103 (1985) 179.

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Graphical Abstract

Four centers of chirality—2 × C, 1 × N, 1 × Mo—are present in the title compound 1, R^* = (R)-1-CHMePh. Complex 1 is characterized, among other things, by a slightly bent CO group, which is in close contact to Rh. A complicated series of ring openings and epimerizations is suggested as a plausible route to 1.

References

1 J. D. Morrison (Ed.): Asymmetric Syntheses. Vol. 5, Academic Press, London 1985.
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4 Type B (310/25 mm) LiChroprep Si60 (40–63 μm), toluene/ether 50:1.
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5 3a/3b: IR (cyclohexane): v̄(CO) = 1940, 1850 cm⁻¹; ¹H-NMR (250 MHz, [D₈]toluene), 100°C: δ = 1.59 (d, 3H, J = 6.8 Hz, CHCH₃), 3.11 (m, 1 H, CH₃CH), 3.72 (d, 1H, J = 6.9 Hz, MoCH), 5.29 (m, 1H, NH), 4.89 (s, 5H, Cp), 6.26–7.96 (m, 9H, phenyl and pyridyl).- 3a, −70°C: δ = 1.51 (d, 3H), 3.04 (m, 1H), 3.67 (d, 1H), 5.38 (m, 1H), 4.70 (s, 5H), 6.18–7.86 (m, 9H).- 3b, −70°C: δ = 4.91 (s, Cp).- 3c/3d: IR (cyclohexane): v̄(CO) = 1940, 1850 cm⁻¹; ¹H-NMR (250 MHz, [D₈]toluene), 100°C: δ = 1.21 (d, 3H, J = 6.7 Hz, CHCH₃), 3.06 (m, 1H, CH₃CH), 3.76 (d, 1H, J = 7.2 Hz, MoCH), 5.37 (m, 1H, NH), 4.75 (s, 5H, Cp), 6.38–8.02 (m, 9H, phenyl and pyridyl).- 3c, −70°C: δ = 1.05 (d, 3H), 2.51 (m, 1H), 3.61 (d, 1H), 5.30 (m, 1H), 4.59 (s, 5H), 6.27–7.93 (m, 9H).- 3d, −70°C: δ = 4.67 (s, Cp).
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6 3a: Space group P2₁2₁2₁, a = 10.084(2), b = 13.516(2), c = 29.203(5) Å, Z = 8 (two independent molecules), 7237 reflections (Mo_κα radiation, 2 0_max = 63°C), η = 1.06(7), R_w = 0.036.- 3c: space group P2₁2₁2₁, a = 6.795(1), b = 11.744(2), c = 24.110(3) Å, Z = 4, 4422 reflections (2 θ_max = 63°), η = − 1.19(9) for the opposite configuration, R_w = 0.029.- 4a: space group P2₁2₁2₁, a = 8.948(2), b = 14.048(3), c = 20.007(4) Å, Z = 4, 4479 reflections (2 θ_max = 55°), η = 1.05(9), R_w = 0.034. Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG) on quoting the depository number CSD-51778, the names of the authors, and the full citation of the journal.
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9 4: 0.2 mmol 3a/3b, 0.1 mmol [Rh(nbd)Cl]₂, 100 mg KOH, catalytic amounts of [18]crown-6 (toluene, 2 h, 20°C). Chromatography on Al₂O₃, neutral without added water with toluene/ether 6 :1.
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10 4a/4b: IR (cyclohexane): v̄(CO) = 1915 s, 1835 m, 1815w sh cm⁻¹; ¹HNMR (250 MHz, [D₈]toluene), 100°C: δ = 1.19 (s, 2H, nbd), 1.20 (d, 3H, J = 6.9 Hz, CHCH₃), 3.21 (q, 1H, CH₃CH), 3.48 (m, 2H, nbd), 3.57 (m, 3H, MoCH + nbd), 3.72 (m, 2H, nbd), 4.97 (s, 5H, Cp), 6.03–7.76 (m, 9H, phenyl and pyridyl).-4a, −70°C: δ = 0.9 (d, 3H), 1.17 (s, 2H), 2.87 (m, 1H), 3.29 (s, 1H), 3.40, 3.57, 3.83 (m, 6H), 4.82 (s, 5H), 5.83–7.94 (m, 9H).-4b, −70°C: δ = 5.30 (s, Cp).
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11 Priority sequence used for the specification of the Mo configuration:Cp> N(MoNC ring)> C(MoNC ring), looking at the molecule from the side opposite to the two carbonyl groups. Cf. H. Brunner, Adv. Organomet. Chem. 18 (1980) 195.
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Volume25, Issue4

April 1986

Pages 371-373

[Cp(CO)₂Mo{NR^*[Rh(norbornadiene)]-CH(pyridyl)}], a Rhodium Complex with an Asymmetric Molybdenum Atom in the Chelate Skeleton^†

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[Cp(CO)2Mo{NR*[Rh(norbornadiene)]-CH(pyridyl)}], a Rhodium Complex with an Asymmetric Molybdenum Atom in the Chelate Skeleton†

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[Cp(CO)₂Mo{NR^*[Rh(norbornadiene)]-CH(pyridyl)}], a Rhodium Complex with an Asymmetric Molybdenum Atom in the Chelate Skeleton^†