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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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slide1

Pn Ligand Complexes of Manganese

CpBIG and Mn – A Good Combination

slide2

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.

slide3

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.

slide4

[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
slide5

[CpRMn(cht)] as Precursor (cht = cycloheptatriene)

thermal displacementellipsoidsat 50% probabilitylevel

slide6

[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.

slide7

[CpRMn(cht)] as Precursor (cht = cycloheptatriene)

  • eclipticconformationofCpBIGligands

thermal displacementellipsoidsat 50% probabilitylevel

slide8

[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.

slide9

[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
slide10

[CpRMn(CO)3] as Precursor

  • binuclearcomplexisevenmorestablethanmononuclearone
  • P4ligandandMnatomsshieldedbybulkyCpBIGligands
slide11

[CpRMn(CO)3] as Precursor

D≈ 0.06 Å

D≈ 0.1 Å

thermal displacementellipsoidsat 50% probabilitylevel

slide12

[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.

slide13

Summary

  • fournewPnligandcomplexesofmanganeseandappropriatestartingmaterialsweresynthesized
  • different structuralmotifscomparedtosmallerCpRligands
  • stabilizationof neutral Mncomplexeswithtetrahedro-P4ligands
slide14

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)