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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
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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
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Gábor BalázsUniversity of Regensburg
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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
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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
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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
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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.
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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.
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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
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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
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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.
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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 –
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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
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ICOMC 2010
W–P 2.142(1) Å
31P NMR: δ = -188 ppm31P NMR: δ = 1239 ppm
W–As 2.258(1) Å
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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
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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
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ICOMC 2010
N WN
N
P
N
Me3SiSiMe3
SiMe3N WN
N
P
N
Me3SiSiMe3
SiMe3
Se
+ Se ·
Toluene, rt.
quantitative yield
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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
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ICOMC 2010
31P{1H} NMR
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DFT Optimized (RI-DFT, BP86, SV(P)) Transition State Structure
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ICOMC 2010
N WN
N
P
N
Me3SiSiMe3
SiMe3N W
N
N
P
N
Me3SiSiMe3
SiMe3
Se
+
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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)
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Single Marks
N WN
N
E
N
Me3SiSiMe3
SiMe3
Q
N WN
N
E
N
Me3SiSiMe3
SiMe3
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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)
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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)
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N WN
N
As
N
Me3SiSiMe3
SiMe3
S
Molecular Orbital Interaction Diagram
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ICOMC 2010
N WN
N
As
N
Me3SiSiMe3
SiMe3
S
Molecular Orbital Interaction Diagram
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Comparative MO Diagram in Complexes N3NW(PQ)
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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
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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)
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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)
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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
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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