gábor balázs university of regensburg icomc 2010 dr. max mustermann referat kommunikation &...

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Dr. Max MustermannReferat Kommunikation & Marketing Verwaltung

Gábor BalázsInstitute of Inorganic ChemistryUniversity of Regensburg

COMPLEXES WITH TERMINALLY

COORDINATED EQ (E = P, As; Q = S, Se, Te)

LIGANDS

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Contents

• Introduction

• Complexes with W≡E (E = group 15 element) triple bonds

• Synthesis of complexes with linearly coordinated EQ ligands (Q = group 16 element)

• Reactivity of linearly coordinated EQ Complexes

• Summary

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N O N O

O

N

LnM

LnM

ON

MLnLnM

ON

MLnLnM

LnMN

O

P O P O

EQE = P, As, Sb, BiQ = O, S, Se, Te

Coordination modes of NO

Gábor BalázsUniversity of Regensburg

ICOMC 2010

LnM + EQ

Q

E

LnME = P, As, Sb, BiQ = O, S, Se, Te

Possible synthetic roots for complexes with η1-EQ ligands

Gábor BalázsUniversity of Regensburg

ICOMC 2010

O. J. Scherer, J. Braun, P. Walther, G. Heckmann, G. Wolmershaeuser, Angew. Chem., 103, 1991, 861.O. J. Scherer, C. Vondung, G. Wolmershauser, Angew. Chem. Int. Ed. Engl., 36, 1997, 1303.O. J. Scherer, S. Weigel, G. Wolmershauser, Heteroat. Chem., 10, 1999, 622.J. F. Corrigan, S. Doherty, N. J. Taylor and A. J. Carty, J. Am. Chem. Soc., 116, 1994, 9799.J. E. Davies, M. J. Mays, E. J. Pook, P. R. Raithby, P. K. Tompkin, Chem. Commun., 1997, 1997.C. E. Laplaza, W. M. Davis, C. C. Cummins Angew. Chem. Int. Ed. Engl. 1995, 34, 2042.M. J. A. Johnson, A. L. Odom, C. C. Cummins Chem. Commun., 1997, 1523.

CartyLnMMLn

LnMMLn

P

MLn

O

MLn = Ru(CO)3

CpRNiP

PNiCpR

W Q

Q

(CO)4

Q = O, S

MLn

LnM MLn

P

S

MLn = CpMo(CO)2MLn = CpW(CO)2

Mays

MLn

LnM MLn

P

Q

Q = O, S, Se

P

Q

MLn

LnM MLn

P

Q

P

Q = Se, Te

MLn = Cp''Co; Cp'' = C5H3tBu-1,3 Scherer

Cummins

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Complexes with Terminal Phosphido, Arsido and Antimonido Ligands

Schrock Cummins Scheer

N WN

N

P

N

Me3SiSiMe3

SiMe3

Ph''RNMo

NRPh''

NRPh''

P RO

WRO

RO

P W(CO)5

R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, 2044.C. E. Laplaza, W. M. Davis, C. C. Cummins Angew. Chem. Int. Ed. Engl. 1995, 34, 2042.M. Scheer, K. Schuster, T. A. Budzichowski, M. H. Chisholm, W. E. Streib Chem. Commun. 1995, 1671.

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

P

N

Me3SiSiMe3

SiMe3N WN

N

Cl

N

Me3SiSiMe3

SiMe3 + 2 LiP(H)Ph

R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, 2044.M. Scheer, J. Müller, M. Häser Angew. Chem. 1996, 108, 2637.

Gábor BalázsUniversity of Regensburg

ICOMC 2010

M. Scheer, J. Müller, G. Baum, M. Häser Chem. Commun. 1998, 2505.M. Scheer, J. Müller, M. Schiffer, G. Baum, R. Winter Chem. Eur. J. 2000, 6, 1252.

N

W

N N

EN

R

RR

N WN

N

Cl

N

RR

R + 2 LiE(SiMe3)2

E = Sb, Bi

N

W

NN

N

R

R R

R = CH2C(CH3)3

W-Sb 2.574(1) Å

Gábor BalázsUniversity of Regensburg

ICOMC 2010

13C NMRδ = 319.4 ppm (W≡C)

W(1)-C(19) 1.813(1)Å

N WN

N

C

N

Me3SiSiMe3

SiMe3N WN

N

Cl

N

Me3SiSiMe3

SiMe3

Sb

CH2

H

SiMe3

Li

SiMe3

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

Sb

N

Me3SiSiMe3

SiMe3N WN

N

Cl

N

Me3SiSiMe3

SiMe3

Sb

CH

H

SiMe3Me3Si

Li

G. Balázs, M. Sierka, M. Scheer Angew. Chem. Int. Ed. 2005, 44, 4920.

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Bond lengths (Å) and Angles (°):

Exp. Calc. W – Sb 2.525(2) 2.514 W – Neq 1.994(8) 2.015

W – Nax 2.33(1) 2.516

Neq – W – Sb 101.8(2) 104.1

Nax – W – Sb 180.0 –

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

E

N

RR

RN WN

N

Cl

N

RR

R

iPr

iPr

iPr

iPr

iPr

iPr

R =

+ 2 LiEH2

·

E = P, As

N WN

N

E

N

RR

R

EE

Gábor BalázsUniversity of Regensburg

ICOMC 2010

W–P 2.142(1) Å

31P NMR: δ = -188 ppm31P NMR: δ = 1239 ppm

W–As 2.258(1) Å

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N

WN

NN

R

RP

iPr

iPr

iPr

iPr

iPr

iPr

II

N WN

N

P

N

RR

R+ I2

·

W–P 2.544(3) ÅW–I 2.7434(9) ÅP–I 2.729(3) and 2.795(3) Å

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

E

N

Me3SiSiMe3

SiMe3N WN

N

E

N

Me3SiSiMe3

SiMe3

S

S

E = P, As

G. Balázs, J. C. Green, M. Scheer Chem. Eur. J. 2006, 12, 8603.G. Balázs, J. C. Green, D. M. P. Mingos Eur. J. Inorg. Chem. 2007, 2443.

31P NMR: δ = 342.3 ppm; 1JPW = 771.5 Hz

31P NMR: δ = 1080.3 ppm; 1JPW = 138 Hz

Terminally Coordinated EQ Complexes

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

P

N

Me3SiSiMe3

SiMe3N WN

N

P

N

Me3SiSiMe3

SiMe3

Se

+ Se ·

Toluene, rt.

quantitative yield

Gábor BalázsUniversity of Regensburg

ICOMC 2010

31P{1H} NMR

N WN

N

P

N

Me3SiSiMe3

SiMe3

Te

N WN

N

P

N

Me3SiSiMe3

SiMe3

Se

1JPSe = 790 Hz1JPW = 727 Hz

1JPTe = 1759 Hz1JPW = 649 Hz

Gábor BalázsUniversity of Regensburg

ICOMC 2010

31P{1H} NMR

Gábor BalázsUniversity of Regensburg

ICOMC 2010

DFT Optimized (RI-DFT, BP86, SV(P)) Transition State Structure

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

P

N

Me3SiSiMe3

SiMe3N W

N

N

P

N

Me3SiSiMe3

SiMe3

Se

+

Gábor BalázsUniversity of Regensburg

ICOMC 2010

P As

S Se Te S

W–E 2.158(1) 2.152(1) 2.159(1) 2.256(1)

E–Q 1.940(2) 2.081(1) 2.294(1) 2.048(2)

W–E–Q 177.1(4) 177.3(1) 176.6(1) 177.6(1)

Nax–W–E 178.0(4) 178.3(1) 177.8(1) 178.7(2)

Selected bond lengths (Å) and angles (°)

(N3N)W ≡ E

W–P 2.162(4)W–As 2.290(1)

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Single Marks

N WN

N

E

N

Me3SiSiMe3

SiMe3

Q

N WN

N

E

N

Me3SiSiMe3

SiMe3

Gábor BalázsUniversity of Regensburg

ICOMC 2010

P As Sb Bi−482 −429 −333 −293

σ W-E-Q Hybrid.E = P sp0.5 E = Bi sp0.7

σ W-E Hybrid.E = P sp3.3 E = Bi sp6.6

N WN

N

E

N

Me3SiSiMe3

SiMe3

Q

N WN

N

E

N

Me3SiSiMe3

SiMe3

Q P As Sb Bi

O −415 −341 −259 −204

S −401 −339 −262 −207

Se −400 −339 −259 −205

Te −401 −340 −261 −208

W–E Bond Dissociation Energies (kJ·mol−1)

W–E Bond Dissociation Energies (kJ·mol−1)

Gábor BalázsUniversity of Regensburg

ICOMC 2010

O S Se Te

P -558 -349 -287 -212

As -439 -302 -255 -197

Sb -383 -281 -244 -190

Bi -326 -248 -219 -173

E–Q Bond Dissociation Energies (kJ·mol−1)

N WN

N

E

N

Me3SiSiMe3

SiMe3

Q

N WN

N

E

N

Me3SiSiMe3

SiMe3

Q P As Sb Bi

O −415 −341 −259 −204

S −401 −339 −262 −207

Se −400 −339 −259 −205

Te −401 −340 −261 −208

W–E Bond Dissociation Energies (kJ·mol−1)

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

As

N

Me3SiSiMe3

SiMe3

S

Molecular Orbital Interaction Diagram

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

As

N

Me3SiSiMe3

SiMe3

S

Molecular Orbital Interaction Diagram

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Comparative MO Diagram in Complexes N3NW(PQ)

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Q E W–E E–Q

O P 2.12 2.07

As 2.09 1.97

Sb 2.12 2.13

Bi 2.14 2.18

S P 2.22 2.03

As 2.24 1.83

Sb 2.20 2.12

Bi 2.23 2.10

Se P 2.24 1.98

As 2.26 1.82

Sb 2.23 2.09

Bi 2.26 2.08

Te P 2.32 1.92

As 2.33 1.73

Sb 2.28 2.05

Bi 2.30 2.06

P = ,♦ As = , ■ Sb = , ▲ Bi = ●

Hirshfeld Charge Distribution: Positive on W and Negative on Q

Fractional Bond Orders

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

P

N

Me3SiSiMe3

SiMe3

Te

+

N

N

iPr

iPr

iPr

iPr

N

N

iPr

iPr

iPr

iPr

Te + N WN

N

P

N

Me3SiSiMe3

SiMe3

Reactivity of N3NW(PTe)

Gábor BalázsUniversity of Regensburg

ICOMC 2010

N WN

N

P

N

Me3SiSiMe3

SiMe3

Te

+ W

PCy3

PCy3OC

COOC

N WN

N

P

N

Me3SiSiMe3

SiMe3

W

NWN

N

P

N

SiMe3Me3Si

Me3Si

OC

OC CO

CO

Reactivity of N3NW(PTe)

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Conclusions

• Synthesis of complexes containing linearly coordinated EQ ligands of the heavier group 15 and 16 Elements is possible

•The [(N3N)W(PTe) complex can readily be used as a tellurium transfer reagent

• The π system can be best described as two orthogonal three centered two electron system

Gábor BalázsUniversity of Regensburg

ICOMC 2010

Acknowledgment

• Prof. Dr. M. Scheer

• Prof. Dr. J. C. Green

• Prof. Dr. D. M. P. Mingos

• Alexander von Humboldt Foundation

• Deutsche Forschungsgemeinschaft

• University of Regensburg

Thank you for your attention