mono(dinitrogen) and carbon monoxide adducts of bis(cyclopentadienyl) titanium sandwiches
Post on 24-Jan-2016
41 Views
Preview:
DESCRIPTION
TRANSCRIPT
Mono(dinitrogen) and Carbon Monoxide Adducts of
Bis(cyclopentadienyl) Titanium Sandwiches
Tamara E. Hanna, Emil Lobkovsky, and Paul J. Chirik*
J. Am. Chem. Soc. 2006, 128, 6018 - 6019
Ti
R
R
Fe
R = SiMe2But
J. Am. Chem. Soc. 1998, 120, 10264
J. Am. Chem. Soc. 2004, 126, 14688.
Nature 2004, 427, 527.
1: R = SiMe3
2: R = SiMe2Ph3: R = CHMe2
Ti
R
R
1 atm N2
- 45 oCTi N2
above - 45 oC
Ti
R
R
N2
R
R
1: R = SiMe3
2: R = SiMe2Ph3: R = CHMe2
Ti
R
R
Ti N2
above - 45 oC
Ti
R
R
N2
R
R
1 atm N2- 35 oC
TiN2
R
R
N2
Ti
R
R
Ti N2
- 35 oC
R
R
TiN2
R
R
N2
1 atm N2
- 60 oC
1: R = SiMe3
2: R = SiMe2Ph3: R = CHMe2
Ti(1) – N(1) : 2.016(1) Å
N(1) – N(2) : 1.119(2) Å
Ti(1) – N(1) : 2.043(1) Å
N(1) – N(2) : 1.110(2) Å
J. Am. Chem. Soc. 2004, 126, 14688.
J. Am. Chem. Soc. 2000, 122, 6476.
Ti
R
R
TiCO
R
R
CO
1: R = SiMe3
2: R = SiMe2Ph3: R = CHMe2
Ti(1) – C(10) : 1.9786(19) Å
C(10) – O(1) : 1.151(2) Å
Ti(1) – C(13) : 2.0065(18) Å
C(13) – O(1) : 1.150(2) Å
TiCO
R
R
+ tBuNC TiCO
R
R
CNtBu
σ-donating, weakly π-acidic
N2
top related