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P n Ligand Complexes of Manganese Cp BIG and Mn – A Good Combination

P n Ligand Complexes of Manganese Cp BIG and Mn – A Good Combination. Introduction. Selected coordination modes for P n ligands :. review articles: M. Scheer, G. Balazs, A. Seitz, Chem. Rev . 2010 , 110 , 4236-4256.

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P n Ligand Complexes of Manganese Cp BIG and Mn – A Good Combination

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  1. Pn Ligand Complexes of Manganese CpBIG and Mn – A Good Combination

  2. Introduction Selected coordinationmodesforPnligands: review articles: M. Scheer, G. Balazs, A. Seitz, Chem. Rev. 2010, 110, 4236-4256. B. M. Crossairt, N. A. Piro, C. C. Cummins, Chem. Rev.2010, 110, 4164-4177. M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev.2010, 110, 4178-4235.

  3. Introduction • verybulky • negative chargedelocalized •  electron-poorligand • goodsolubilityofobtainedcomplexes G. Dyker, J. Heiermann, M. Miura, J.-I. Inoh, S. Pivsa-Art, T. Satoh, M. Nomura, Chem. Eur. J. 2000, 6, 3426-3433. C. Ruspic, J. R. Moss, M. Schuermann, S. Harder, Angew. Chem., Int. Ed. 2008, 47, 2121-2126.

  4. [CpRMn(cht)] as Precursor (cht = cycloheptatriene) • distortedMn4P4cubeor • fourtimescappedMn4tetrahedron • no Wade-Cluster • 31P{1H} (CD2Cl2): • δ[ppm] = 1079.8 (s, br, ω≈ 170 Hz) • noreaction in thf, toluene, xylene •  high-boilingdibisneeded • dib = 1,3 diisopropylbenzene

  5. [CpRMn(cht)] as Precursor (cht = cycloheptatriene) thermal displacementellipsoidsat 50% probabilitylevel

  6. [CpRMn(cht)] as Precursor (cht = cycloheptatriene) • cyclo-P5asmiddle deck • 31P{1H} (CD2Cl2): δ[ppm] = 396.4 (s, br, ω≈ 500 Hz) • third neutral triple-deckercomplexwithcyclo-P5ligand •  [(Cp*Cr)2(m,h5:5-P5)] : 31P{1H} (C6D6): δ[ppm] = -290.5 (s) •  [(CpCr)2(m,h5:5-P5)] : 31P{1H} (C6D6): δ[ppm] = -100.5 (s) O. J. Scherer, J. Schwalb, G. Wolmershäuser, W. Kaim, R. Gross, Angew. Chem. Int. Ed. 1986, 25, 363-364.

  7. [CpRMn(cht)] as Precursor (cht = cycloheptatriene) • eclipticconformationofCpBIGligands thermal displacementellipsoidsat 50% probabilitylevel

  8. [CpRMn(CO)3] as Precursor neutral cationic M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. Rev. 2010, 110, 4178. I. de los Rios, J.-R. Hamon, P. Hamon, C. Lapinte, L. Toupet, A. Romerosa, M. Peruzzini, Angew. Chem. Int. Ed. 2001, 40, 3910. M. Peruzzini, L. Marvelli, A. Romerosa, R. Rossi, F. Vizza, F. Zanobini, Eur. J. Inorg. Chem. 1999, 931. P. Dapporto, S. Midollini, L. Sacconi, Angew. Chem. Int. Ed. 1979, 18, 469. P. Dapporto, L. Sacconi, P. Stoppioni, F. Zanobini, Inorg. Chem. 1981, 20, 3834. T. Groeer, G. Baum, M. Scheer, Organometallics1998, 17, 5916.

  9. [CpRMn(CO)3] as Precursor • CpR = Cp, Cp* noreactionwith P4 • DFT calculationspredict a higher • stabilityforCp derivative • 31P{1H}(C6D6) • δ[ppm] : -489.8 (d, 3P), -302.7 (q, 1P) • 1JPP= 224 Hz • free P4(C6D6): δ [ppm] = -519.6

  10. [CpRMn(CO)3] as Precursor • binuclearcomplexisevenmorestablethanmononuclearone • P4ligandandMnatomsshieldedbybulkyCpBIGligands

  11. [CpRMn(CO)3] as Precursor D≈ 0.06 Å D≈ 0.1 Å thermal displacementellipsoidsat 50% probabilitylevel

  12. [CpRMn(CO)3] as Precursor 31P{1H} EXSY Measurements: MnP4 Mn2P4 MnP4 Mn2P4 ΔG‡298K= 13.7(5) kcal·mol–1 ΔH‡298K= 11.9(5) kcal·mol–1 ΔS‡298K= –6(1) cal·mol–1·K–1 ΔG‡298K= 13.6(5) kcal·mol–1 ΔH‡298K= 10.7(5) kcal·mol–1 ΔS‡298K= –10(1) cal·mol–1·K–1 V. Mirabello, M. Caporali, V. Gallo, L. Gonsalvi, D. Gudat, W. Frey, A. Ienco, M. Latronico, P. Mastrorilli, M. Peruzzini, Chem.Eur.J. 2012, 18, 11238-11250.

  13. Summary • fournewPnligandcomplexesofmanganeseandappropriatestartingmaterialsweresynthesized • different structuralmotifscomparedtosmallerCpRligands • stabilizationof neutral Mncomplexeswithtetrahedro-P4ligands

  14. Thanksto: • Prof. Dr. M. Scheer • Prof.PieroMastrorilli, Dr. Vito Gallo • (Dynamic NMR Investigations) • Prof. Alexey Timoshkin • (DFT Calculations) • Dr. Eugenia Peresypkina • (X-ray Structures) • Scheer Group • Fonds der Chemischen Industrie • (Financial Support)

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