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