Investigation of CO2 insertion into lanthanide amides

University of New MexicoUNM Digital Repository

Chemistry ETDs Electronic Theses and Dissertations

2-9-2010

Investigation of CO2 insertion into lanthanideamides, alkoxides, and mixed amide/alkoxidesLeigh Anna M. Ottley

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Recommended CitationOttley, Leigh Anna M.. "Investigation of CO2 insertion into lanthanide amides, alkoxides, and mixed amide/alkoxides." (2010).https://digitalrepository.unm.edu/chem_etds/46

INVESTIGATION OF CO2 INSERTION INTO LANTHANIDE AMIDES, ALKOXIDES, AND MIXED AMIDE/ALKOXIDES

LEIGH ANNA M. OTTLEY

BACHELORS OF SCIENCE IN CHEMISTRY University of New Mexico

THESIS

Submitted in Partial Fulfillment of the Requirements for the Degree of

Master of Science

Chemistry and Chemical Biology

The University of New Mexico Albuquerque, New Mexico

December, 2009

To my loving family and friends for their encouragement and support throughout all my endeavors.

ACKNOWLEDGEMENTS

I would like to thank my advisor, Professor Rick Kemp, for his support and direction

over the course of my academic career, as well as my mentor, Dr. Timothy J. Boyle, who

has helped me get where I am today both academically and professionally. I would also

like to thank Dr. Diane Dickie, Dr. Constantine Stewart, and Dr. Todd Alam for their

contributions and guidance. In addition, I would like to thank Dr. Bernadette Hernandez-

Sanchez for invaluable conversations and advice. Finally, I would like to thank the Boyle

group for their hard work and continuous support.

LEIGH ANNA M. OTTLEY

ABSTRACT OF THESIS

Submitted in Partial Fulfillment of the Requirements for the Degree of

Masters of Science

Chemistry and Chemical Biology

The University of New Mexico Albuquerque, New Mexico

December, 2009

Leigh Anna M. Ottley

B.S., Chemistry, University of New Mexico, 2006

M.S., Chemistry and Chemical Biology, University of New Mexico, 2009

ABSTRACT

A novel set of lanthanide (Ln) alkoxycarbonates, [Ln(!-CO2-DBP)(DBP)2]2

where Ln = lanthanide; and DBP = OC6H3-2,6-C(CH3)3, were isolated from a systematic

study of the insertion of CO2(g) (referred to as CO2) into the Ln-O bonds of a series of

new lanthanide alkoxides, Ln(OR)3. This study was undertaken to determine if the

deleterious metal carbonate [M(CO3)y] formation that promotes higher thermal budgets

during processing could be avoided. While processing controls can reduce the formation

of the M(CO3)y phases, this is not always effective, and preventing the formation of these

phases is of interest. Since CO2 insertion into transition metal alkoxides has been

extensively studied and many structures reported, this research focused on CO2 insertion

into the less-studied Ln-O bonds of Ln(OR)3. Initially a series of lanthanide amides

[Ln(NR2)3 where R = SiMe3 and Ln = Ce (1), Sm (2), Dy (3), Yb (4), and Lu (5)] were

synthesized following established routes.4-6 Subsequent conversion of the Ln(NR2)3

species into a series of Ln(OR)3 was achieved by an amide/alcohol exchange route

resulting in Ln(DBP)3 (Ln = Ce (6), Sm (7), Dy (8), Yb (9), and Lu (10); DBP = 2,6-di-

tert-butylphenoxide).7, 8 Once isolated, CO2 at low pressure (<5 psig) and ambient

temperature was introduced to the Ln(OR)3 species to form a novel family of lanthanide

alkoxycarbonate compounds identified as [Ln(!- O2C-DBP)(DBP)2]2 (Ln = Ce (11), Sm

#!!!""

(12), Dy (13), Yb (14), and Lu (15)). Surprisingly, CO2 did not insert into all of the Ln-

O bonds, indicating that this process might be more controllable than initially expected.

Higher-pressure CO2 experiments yielded the same carbonate compounds. Further

manipulation of the ligand set, as a means to control CO2 insertion, was explored by

using a mixed amide/alkoxide precursor generated in situ. This resulted in the formation

of an unusual complex, Sm4(!-CO3)2(!-O)2(DBP)4(THF)2(!-DBP) (16). From this

fundamental study, it has been shown that the ligand may be able to impact the degree of

CO2 insertion into Ln-O bonds. The synthesis and characterization of 1 - 16, as well as

future implications of this work, will be discussed in detail.

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O= !;>DGZXK>8G;*

1.1 M(OR)x Precursors Conversion to M(CO3)y

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1.2 Interest of CO2 Insertion into Lanthanide Complexes

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1.3 Mechanisms of CO2 Insertion into Bonds

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7$#.(!.J6-#K!),&6I+'!P6$5&((-#K!/vide infra1M!N,&6&*$6&8!J#.&6()+#.-#K!,$C8!C,&6&8!+#.!

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5+#!7&!&3P'$-)&.!)$!5$#)6$'!),-(!6&+5)-%-)4M!<=>*,+(!7&&#!*$J#.!)$!-#(&6)!-#)$!(&%&#!)4P&(!

$*!I&)+';&'&I&#)!/O;c1!7$#.(!C,&6&!c!D!G8!<8!T8!=8!A8!R-!$6!+#$),&6!I&)+'8!)$!*$6I!C,+)!

-(!5$#(-.&6&.!),&!#$6I+'!-#(&6)-$#!P6$.J5)!/)$P1!$6!),&!+7#$6I+'!-#(&6)-$#!P6$.J5)!

/7$))$I1!N+89XD7*O1MH!!N,&!&'&I&#)!+))+5,&.!)$!),&!O!-#!),&!()+6)-#K!I+)&6-+'!.-5)+)&(!

C,+)!),&!-#(&6)-$#!P6$.J5)!7&5$I&(!/i.e.8!-*!c!D!G8!),&#!),&!-#(&6)-$#!P6$.J5)!5+#!7&!),&!

*$6I+)&!$6!I&)+''$5+67$34'-5!+5-.!5$IP'&3E! c!D!<8!5+67$34'+)&!$6!+!+'2$345+67$#4'!

5$IP'&3E!c!D!TE!5+67+I+)&E!c!D!=8!5+67$#+)&1MH!!!!!!!!

+89XD7*O=*<=>!-#(&6)-$#!-#)$!O!;!c!7$#.(M!H*

N,&6&!+6&!I+#4!&3+IP'&(!$*!-#(&6)-$#!-#)$!O;G8!O;<8!O;T8!+#.!O;=!7$#.(!/C,&6&!O!D!

)6+#(-)-$#!I&)+'18!7J)!+!'+5J#+!&3-()(!*$6!0#;T!+#.!&%&#!I$6&!(P&5-*-5+''4!0#;=!7$#.(M!!

! N,&!P6$.J5)(!),+)!+6&!$7)+-#&.!*6$I!-#(&6)-$#!$*!<=>*-#)$!+!O;=L!C,&6&!LD!+'24'!

$6!+64'!+6&!)&6I&.!5+67$#+)$!'-K+#.(!/=><=L18!C,-'&!*$6!L!D!G!-)!C$J'.!7&!)&6I&.!

,4.6$K&#!5+67$#+)$M^;H!!N,6&&!7-#.-#K!I$.&(!,+%&!7&&#!$7(&6%&.!*$6!5+67$#+)$!'-K+#.(!

-#!I$#$!$6!.-#J5'&+6!)6+#(-)-$#!I&)+'!5$IP'&3&(!+1! ^8!71! >8!51! >; >!/+89XD7*-1M!!N,&(&!

+6&!-#!5$IP+6-($#!C-),!),&!C&''!()J.-&.!7$#.-#K!I$.&(!$*!5+67+I+)&!/=><TL>1!'-K+#.(!

I-#J(!+!:>; H!I$.&M^;H!!

!!!!!!

1.4 Families of Lanthanide Compounds Selected for this Study

! N,6&&!(&)(!$*!'+#),+#-.&!5$IP'&3&(!C&6&!(4#),&(-V&.!+#.!5,+6+5)&6-V&.!*$6!),-(!

6&(&+65,h!+I-.&(!e90#/R-O&H1>BHf8!+'2$3-.&(!90#/=L1HB8!!+#.!!I-3&.!+I-.&Y+'2$3-.&(!

t0#/=L19T/R-O&H1>B>uM!!N,&!0#9R-O&H1>BH!C+(!),&!*+%$6&.!+I-.&!.J&!)$!),&!&+(&!-)!5+#!

7&!I&)+()+(-V&.M!R-#5&!),&!+I-.&(!,+%&!+'6&+.4!7&&#!&3P'$6&.!C-),!'-I-)&.!(J55&((8!),&!

)C$!$),&6!'-K+#.!(&)(!/i.e.8!+'2$3-.&(!+#.!+I-.&Y+'2$3-.&(1!C&6&!()J.-&.!-#!)&6I(!$*!<=>*

-#(&6)-$#M>W!!G$C&%&68!7+52K6$J#.!-#*$6I+)-$#!$#!&+5,!$*!),&(&!(P&5-&(!-(!.&)+-'&.!7&'$CM!!!

O=R=O (B8Z7C**

! L+.i2$%!+#.!5$;C$62&6(!-#!^`[F!(4#),&(-V&.!+!(&6-&(!$*!)6-(+I-.$!'+#),+#-.&(!

e0#9T/R-O&H1>Bn,!C,&6&!0#!D!A68!T.8!RI8!cJ8!U7E!n D!>8!Hf!+#.!-#%&()-K+)&.!),&-6!

6&+5)-%-)-&(!C-),!<=>M*>W!!R-#5&!),&!P6$.J5)(!C&6&!#$)!564()+''-#&8!),&4!C&6&!$#'4!

-.&#)-*-&.!J(-#K!_N;SL!(P&5)6$(5$P4M!!N,&(&!-#%&()-K+)-$#(!6&%&+'&.!),+)!),&!I&)+';

+1! 71!

+89XD7*-=*<P! ^8!WP! >8!KP! >; >M!<+67$#+)$!'-K+#.!7-#.-#K!I$.&(!)$!&-),&6!+!I$#$#J5'&+6!$6!.-#J5'&+6!I&)+'!+)$I!M^;H

5$#)+-#-#K!P6$.J5)!C+(!5$#)+I-#+)&.!C-),!+!#JI7&6!$*!(&5$#.+64!P6$.J5)(8!-#5'J.-#K!

-($54+#+)&!/O&HR-T<=18!(-'$3+#&!9/O&HR-1>=B8!+#.!7-(/)6-I&),4'(-'4'15+67$.--I-.&!

/O&HR-TD<DTR-O&H1!(P&5-&(M!!!L&5&#)'48!<=>!-#(&6)-$#!$*!<&9T/R-O&H1>BH!C+(!()J.-&.!

J#.&6!+#!+6K$#!+)I$(P,&6&!+)!^]al<!+#.!*$J#.!)$!4-&'.!+#!+I$6P,$J(!5$IP$J#.!

-.&#)-*-&.!+(!t<&W9T/R-O&H1>B^>/<=>1ZMu!>]!!!N,-(!5$J'.!$#'4!7&!5,+6+5)&6-V&.!74!_N;SL!

+#.!&'&I&#)+'!+#+'4(-(!(-#5&!-)!C+(!#$)!+!564()+''-#&!P6$.J5)M!!S#!),&!P6&%-$J(!6&(&+65,8!

-($'+)-$#!$*!564()+'!()6J5)J6&(!)$!+55J6+)&'4!J#.&6()+#.!),&!P6$.J5)(!5$J'.!#$)!7&!6&+'-V&.!

*$6!),&(&!P+6)-5J'+6!+I-.&(!7J)!$),&6!0#;TL>!<=>!-#(&6)-$#!()6J5)J6&(!C&6&!$7)+-#&.!+(!

.-(5J((&.!-#!<,+P)&6!>M!G&#5&8!),&!-#%&()-K+)-$#!$*!<=>!-#(&6)-$#!-#!0#9T/R-O&H1>BH!C+(!

#$)!P&6*$6I&.!*$6!),-(!()J.4!7J)!C+(!-#()&+.!J(&!+(!P6&5J6($6(!*$6!(J7(&XJ&#)!5$#%&6(-$#!

)$!0#/=L1HM!!

O=R=- (?]GJ8Z7C*

! N$!()J.4!<=>*-#(&6)-$#(!-#)$!0#;=!7$#.(!$*!+'2$3-.&(8!+!C&'';5,+6+5)&6-V&.8!

()6J5)J6+''4!(-I-'+6!(&6-&(!$*!-.&#)-5+''4;'-K+)&.!0#/=L1H!(P&5-&(!C+(!6&XJ-6&.M!!

"I-.&Y+'5$,$'4(-(!,+(!P6$%&#!)$!7&!),&!I$()!&**&5)-%&!+#.!%&6(+)-'&!6$J)&!*$6!),&!

P6$.J5)-$#!$*!0#/=L1H 5$IP$J#.(!if!),&!0#/TL>1H!P6&5J6($6!-(!*6&&!$*!+'2+'-!I&)+'!(+')!

5$#)+I-#+)-$#M!R4#),&(&(!$*!),&!0#9T/R-O&H1>BH!P6&5J6($6(!C&6&!J#.&6)+2&#!+55$6.-#K!)$!

2#$C#!'-)&6+)J6&!P6$5&.J6&(!74!6&+5)-#K!'+#),+#-.&!,+'-.&(!/0#dH1!C-),!P$)+((-JI!

7-()6-I&)4'(-'4'+I-.& 9vT/R-O&H1>B!/7^*O1M!N,&!&35,+#K&!C-),!+'5$,$'(!/7^*-1!J(J+''4!

P6$5&&.(!6+P-.'4!+#.!5+#!7&!.$#&!-#!%+6-&)4!$*!$6K+#-5!($'%&#)(!+)!'$C!)&IP&6+)J6&!+#.!

C+(!),&6&*$6&!J(&.!)$!(4#),&(-V&!0#/=L1HM!!

/;5Q*_*Q*4"N%827QP-*****************************/;`"N%827QP-aQ*_*Q*45Q**********************************`Oa*

!/;`"N%827QP-aQ*_*Q*0b).*****************/;N).PQ*_*Q*0b"N%827QP-**************************`-a*

(*c*<?]<?8*B7><?*N/83*4*GD*"<Pd*5*c*AD*GD*,?**

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+PP6$P6-+)&!+I-.&!),+)!6&(J')&.!-#!+!),6&&;5$$6.-#+)&!0#/?@A1H!90#D<&!/M18[!RI!/T18!?4!

/U18Z!U7!/V18!+#.!0J!/OL1B!5$IP'&3M!!N,-(!'-K+#.!C+(!5,$(&#!.J&!)$!-)(!()&6-5!7J'2!),+)!

+''$C(!*$6!'$C&6&.!5$$6.-#+)-$#!+6$J#.!),&!I&)+'!5&#)&68!&+(&!$*!564()+''-V+)-$#8!+#.!),&!

*$6I+)-$#!$*!I$#$I&6-5!(P&5-&(!+56$((!),&!0#!(&6-&(M!!O$#$I&6-5!(P&5-&(!C&6&!$*!

-#)&6&()!)$!2&&P!),&!P$((-7'&!%+6-+7'&(!)$!+!I-#-IJI!.J6-#K!),&!-#(&6)-$#!6&+5)-$#(M!

S#56&+(-#K!),&!#J5'&+6-)4!$*!),&!I$'&5J'&!5$J'.!-)(&'*!+**&5)!),&!-#(&6)-$#!$J)5$I&M!"!

(-I-'+6!.-()$6)&.!)6-K$#+'!P'+#+6!+66+#K&I&#)!$*!M*j!OL*+''$C&.!*$6!),&!&3P'$6+)-$#!$*!

5+)-$#!(-V&!&**&5)(!$#!),&!6&+5)-%-)4!$*!<=>!C-),!0#/=L1HM!!

O=R=Q 28J7Z*(B8Z76(?]GJ8Z7C*

! _J6),&6!-#%&()-K+)-$#!$*!),&!(&'&5)-%-)4!$*!<=>*-#(&6)-$#!-#)$!0#;T!$6!0#;=!7$#.(!

5$#5&#)6+)&.!$#!(4#),&(-(!$*!I-3&.!+I-.&Y+'2$3-.&!P6&5J6($6(!/7^*Q1M!!G$C&%&68!JP$#!

-($'+)-$#8!),&!P6&5J6($6(!P,+(&;(&P+6+)&.!-#)$!C,+)!+PP&+6(!)$!7&!),&!),&6I$.4#+I-5+''4;

()+7'&!,$I$'&P)-5!P6$.J5)(!9i.e.8!0#/TL>1H!+#.!0#/?@A1HBM!N,&6&*$6&8!)$!+%$-.!),-(!

P6$7'&I8!),-(!5$IP$J#.!C+(!K&#&6+)&.!in-situ!+#.!(J7(&XJ&#)!6&+5)-$#!C-),!<=>*C+(!

),&#!J#.&6)+2&#M!!!

/;`"N%827QP-aQ*_*n*0b1A\*****************/;`"N%827PQa-N1A\P*_*0b"N%827QP-***********`Qa*

n*c*O*

1.5 Summary

N,&! *$5J(! $*! ),-(! ),&(-(! -(! )$! .&%&'$P! ),&! *J#.+I&#)+'! J#.&6()+#.-#K! $*! <=>!

-#(&6)-$#!5$IP$J#.(!+(! -)! 6&'+)&(! )$! ),&!5+)-$#!(-V&!$*! ),&!0#/=L1HM!N,&!P6&%-$J(!C$62!

.$#&!$#!),&(&!(4()&I(!-(!.&(56-7&.!-#!<,+P)&6!>!/vide infra1M!!N$!+5,-&%&!),&!()+)&.!K$+'8!

+! (&6-&(!$*! ()6J5)J6+''4;(-I-'+6!0#/=L1H!P6&5J6($6(! ),+)! -#(&6)!<=>!+#.!4-&'.! 564()+''-#&!

P6$.J5)(! -(! #&5&((+64M! ! N,&! (4#),&(&(! +#.! 5,+6+5)&6-V+)-$#(! $*! 0#9T/R-O&H1>BH8!

0#/?@A1H8! t0#9T/R-O&H1>B>/?@A18u! +#.! ),&! (J7(&XJ&#)! <=>! -#(&6)-$#! P6$.J5)(! +6&!

.&(56-7&.!-#!.&)+-'!-#!<,+P)&6!HM!!S)!C+(!&3P&5)&.!),+)!<=>*C$J'.!6&+.-'4!+#.!*J''4!-#(&6)!

-#)$! ),&! 0#;=! 7$#.(M! ! N,&! (&'&5)-$#! $*! +! (4()&I! ),+)! C-''! 4-&'.! 564()+''$K6+P,-5+''4!

5,+6+5)&6-V+7'&!(P&5-&(!)$!J#&XJ-%$5+'!-.&#)-*4!),&!*-#+'!P6$.J5)(!-(!%&64!-IP$6)+#)M! ! !S#!

+..-)-$#8!-)!C+(!$*!-#)&6&()!)$!-($'+)&!I-3&.Y+I-.&!+'2$3-.&(!*$6!<=>*-#(&6)-$#M!!N,-(!-(!+!

%&64! 5,+''&#K-#K!P6$7'&I8! (-#5&! ;T/R-O&H1>! -(! 2#$C#! )$!7&! +! K$$.! '&+%-#K!K6$JPM>F8! >Z!

N,&6&*$6&8!+')&6#+)-%&!6$J)&(!)$!()J.4!<=>!-#(&6)-$#!-#)$!,&)&6$'&P)-5!'-K+)&.!(P&5-&(!#&&.(!

)$! 7&! .&%&'$P&.M! ?-(5J((-$#! $*! ),&! 6&+($#-#K! 7&,-#.! ),&! %+6-$J(! '-K+#.! (&'&5)-$#! +#.!

P6$5&((-#K!5$#.-)-$#(!&IP'$4&.!-(!P6&(&#)&.!-#!<,+P)&6!WM!!S)!-(!+#)-5-P+)&.!),+)!),&!&3)&#)!

$*!C,-5,!<=>!-(!+7'&!)$!-#(&6)! -#)$!),&!0#;=!7$#.(!$*!),&(&!(P&5-*-5!5$IP$J#.(!5+#!7&!

.&)&6I-#&.! )$! *J6),&6!.&*-#&! ),-(! 6&+5)-%-)4M! !<,+P)&6!W!+'($!P6&(&#)(! ),&!P$((-7'&! *J)J6&!

.-6&5)-$#(!),+)!5+#!7&!PJ6(J&.!7+(&.!$#!),&!6&(J')(!$7)+-#&.!*6$I!),-(!()J.4M!!!

-= .7F87I*GH*.7?<>7Z*/8>7D<>XD7*

2.1 CO2 Insertion

! N,&!()J.4!$*!<=>*-#(&6)-$#!-#)$!O;c!9O!/)6+#(-)-$#!I&)+'1E!c!/&'&I&#)1!D!G8!T8!

=8!<8!A8!R8!+#$),&6!OB!7$#.(!,+(!7&&#!()J.-&.!*$6!I+#4!4&+6(M^;H!!?J&!)$!),&!+7J#.+#5&!

$*!<=>!-#!),&!+)I$(P,&6&8!I+#4!6&(&+65,!&**$6)(!*$5J(-#K!$#!5,&I-5+'!(&XJ&()6+)-$#!$*!

5+67$#!+6&!J#.&6C+4M>8!H8!^W8!^]8!>[8!>`!!G$C&%&68!),&!7$J#)4!$*!<=>!+'($!P$(&(!+!P6$7'&I!*$6!

5&6+I-5!I+)&6-+'(!P6$5&((-#K8!5+J(-#K!*$6I+)-$#!$*!5+67$#+)&!-#)&6I&.-+)&(!+(!+!6&(J')!$*!

<=>!-#(&6)-$#!-#)$!O;c!7$#.(!+(!P6&%-$J('4!.&(56-7&.M^a;^>!!N,&!I&5,+#-(I(!74!C,-5,!

<=>!-#(&6)(!-#)$!),&(&!7$#.(!+#.!),&!7-#.-#K!I$)-*(!,+%&!7&&#!),$6$JK,'4!6&P$6)&.!-#!),&!

'-)&6+)J6&!*$6!)6+#(-)-$#!I&)+'(!+#.!+6&!6&'+)-%&'4!C&'';J#.&6()$$.M^;H!!!

"(!+!'-K+#.8!<=>!-(!J#-XJ&!-#!),+)!-)!,+(!7$),!#J5'&$P,-'-5!+#.!&'&5)6$P,-'-5!7$#.-#K!

(-)&(8!+''$C-#K!*$6!+!C-.&!6+#K&!$*!5$$6.-#+)-$#!5$IP'&3&(!*6$I!6&+5)-$#!C-),!I&)+'!

(P&5-&(M!!N,&!5,+6+5)&6-V+)-$#!$*!),&!*-#+'!P6$.J5)!-(!&3)6&I&'4!-IP$6)+#)8!&(P&5-+''4!

J)-'-V-#K!(-#K'&!564()+'!d;6+4!.-**6+5)-$#8!*$6!),&!&'J5-.+)-$#!$*!<=>!7$#.-#K!I$)-*(!

P6&(&#)!-#!),&!*-#+'!()6J5)J6&(M!S#!5$I7-#+)-$#!C-),!$),&6!+#+'4)-5+'!5,+6+5)&6-V+)-$#!

I&),$.(!(J5,!+(!IJ')-#J5'&+6!I+K#&)-5!6&($#+#5&!/TOL18!&'&I&#)+'!+#+'4(-(!/c"18!

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.&)&6I-#+)-$#(!/IP18!)$!#+I&!+!*&C8!5,+6+5)&6-V-#K!),&!*-#+'!P6$.J5)(!5+#!7&!.$#&!C-),!

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4-&'.!5+67+I+)&(!,+%&!7&&#!C&'';6&P$6)&.!-#!),&!'-)&6+)J6&M^H;^]8!Ha;H[!!N,&6&!+6&!)C$!

5$II$#!6&+5)-$#!6$J)&(!J(&.!)$!(4#),&(-V&!),&(&!5$IP$J#.(h!-1!6&+5)-$#!$*!+#,4.6$J(!

I&)+'!,+'-.&(!/Ody1 C-),!+!%+6-&)4!$*!+I-#&(!/GTL>1!-#!),&!P6&(&#5&!$*!<=>8!!$6!--1!

6&+5)-$#!$*!O/TL>1x!C-),!<=>!%+P$6(!*6$I!.64!-5&!$6!<=>!7J77'&.!-#)$!),&!6&+5)-$#MH!!"!

*&C!6&P6&(&#)+)-%&!I&)+'!5+67+I+)&(!9O/=><TL>1yB!$7)+-#&.!J(-#K!),&!*-6()!(4#),&)-5!

6$J)&!-#5'J.&!K6$JP!Sg!)6+#(-)-$#!I&)+'(!5+67+I+)&(8!O/=><TL>1W!/C,&6&!O!D!N-8!r68!$6!

G*E!L!D!c)!$6!A6i18!K6$JP!g!5+67+I+)&(!9O/=><TL>1nB!/C,&6&!O!D!T7!$6!N+8!L!D!c)8!n!D!

]E!O!D!T78!L!D!c)8!A6i8!n!D!W18!+#.!K6$JP!gS!5+67+I+)&(!9O>/=><Tc)>1WB!/C,&6&!O!D!<6!

$6!O$1MH`8Ha8!Wa!!S#!+..-)-$#8!(&%&6+'!I+-#!K6$JP!5$IP'&3&(!(J5,!+(!R#9=><T/A6i1!>BW!+#.!

"'>9=><T/A6i1 >BF!C&6&!$7)+-#&.!J(-#K!),-(!6$J)&M!H[;W^!!L&P6&(&#)+)-%&!&3+IP'&(!$*!

O/=><TL>1y!5$IP'&3&(!(4#),&(-V&.!J(-#K!),&!(&5$#.!6$J)&!-#5'J.&!K6$JP!^W!+#.!^]!

5$IP'&3&(!R#/=><TL>1W!/C,&6&!L!D!c)1!+#.!R7/=><TL>1H!/C,&6&!L!D!O&8!c)8!A6i1MHW!!S#!

+..-)-$#8!)6+#(-)-$#!I&)+'!N-!+#.!<6!5+67+I+)&(!,+%&!7&&#!$7)+-#&.!74!),&!6&+5)-$#!$*!

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!R$'J)-$#!()+)&!^H<!e^Gf!TOL!(P&5)6+!*$6!+''!5$IP$J#.(!C&6&!$7)+-#&.!J(-#K!+!]!II!@@!

($'J)-$#!P6$7&!$#!+!@6J2&6!"Od!Waa!OGV!(P&5)6$I&)&6M!"''!(P&5)6+!C&6&!6&*&6&#5&.!

J(-#K!.&J)&6+)&.!)$'J&#&;d8M!R+IP'&(!C&6&!I+.&!JP!-#!+!K'$%&7$3!J(-#K!564()+''-#&!

I+)&6-+'!+#.!),&!(+IP'&!)J7&(!C&6&!*'+I&!(&+'&.!J#.&6!%+5JJI!)$!+%$-.!6&+5)-$#!C-),!),&!

+)I$(P,&6&M!

O&')-#K!P$-#)!.&)&6I-#+)-$#(!/IP1!C&6&!P&6*$6I&.!$#!(&+'&.!(+IP'&(!J(-#K!+#!

c'&5)6$),&6Iy!O&')-#K!A$-#)!"PP+6+)J(M!R+IP'&(!C&6&!P6&P+6&.!-#(-.&!+!K'$%&7$3!74!

'$+.-#K!),&!P$C.&6!-#)$!K'+((!+IPJ'&(!),+)!C&6&!(&+'&.!J(-#K!%+5JJI!K6&+(&!7&*$6&!

6&I$%+'!*6$I!),&!K'$%&7$3M!!

3.1 Amide Synthesis and Characterization

! N,&!(4#),&(&(!*$6!+''!0#9T/R-O&H1>BH!C&6&!J#.&6)+2&#!+55$6.-#K!)$!6&P$6)&.!

P6$5&.J6&(!/7^*O1MW;F8!F]8!FZ!!?J&!)$!),&!(-I-'+6-)4!$*!(4#),&(-(!P6$5&.J6&8!+!K&#&6+'!

P6&P+6+)-%&!6$J)&!)$!0#9T/R-O&H1>BH!!-(!.&(56-7&.!C-),!(P&5-*-5!.&)+-'(!*$6!+!P+6)-5J'+6!

5+)-$#8!(JPP'-&.!7&'$CM!!=#!+!R5,'&#2!'-#&!J#.&6!*'$C-#K!+6K$#8!),&!+PP6$P6-+)&!0#dH!

C+(!+..&.!74!)6+#(*&6;)J7&!$%&6!+!^!,6!P&6-$.!)$!+!()-66-#K!($'J)-$#!$*!vT/R-O&H1>!-#!NG_!

P6&%-$J('4!5$$'&.!)$!az<!*$6!Ha!I-#!-#!+#!-5&!C+)&6!7+),M!/Note:!),-(!6&+5)-$#!5+#!7&!%&64!

&3$),&6I-5!($!5$$'-#K!),&!($'J)-$#!-(!#&5&((+64!)$!5$#)6$'!,&+)!&%$'J)-$#1M!!"*)&6!

5$IP'&)&!+..-)-$#!$*!),&!0#dH8!),&!6&+5)-$#!I-3)J6&!C+(!()-66&.!$%&6!#-K,)!+#.!+''$C&.!)$!

('$C'4!C+6I!)$!6$$I!)&IP&6+)J6&M!!"*)&6!^>!,68!),&!6&+5)-$#!I-3)J6&!C+(!6&I$%&.!*6$I!

),&!7+),!+#.!+!'-XJ-.!#-)6$K&#!(-.&;)6+P!5$##&5)&.M!g$'+)-'&!5$IP$#&#)(!C&6&!6&I$%&.!74!

%+5JJI!.-()-''+)-$#!)$!4-&'.!+!76$C#!/RI8!<&1!$6!$**;C,-)&!/?48!U78!0J1!P$C.&6M!N,-(!

P$C.&6!C+(!6&;.-(($'%&.!-#!,&3+#&(!+#.!5+6&*J''4!)6+#(*&66&.!)$!5&#)6-*JK&!)J7&(M!N,&!

I$),&6!'-XJ$6!C+(!(&P+6+)&.!*6$I!),&!vd!74!5&#)6-*JK+)-$#!4-&'.-#K!+!)6+#(P+6&#)!'-XJ-.M!!

N,-(!C+(!.6-&.!74!%+5JJI!.-()-''+)-$#!)$!$7)+-#!+!76$C#!/<&8!RI1!$6!$**;C,-)&!/?48!U78!

041!P$C.&6M!!c+5,!P$C.&6!C+(!(&P+6+)&'4!'$+.&.!-#)$!+!(J7'-I+)$6!-#(-.&!),&!K'$%&7$38!

C+(!5+6&*J''4!)6+#(*&66&.!)$!),&!R5,'&#2!'-#&!+#.!P'+5&.!J#.&6!%+5JJI!/x^a;H!)$661M!"#!

+5&)$#&Y.64!-5&!I-3)J6&!C+(!P'+5&.!-#!),&!5$'.!*-#K&6!$*!),&!+PP+6+)J(!+#.!(J7'-I+)-$#!

C+(!P&6*$6I&.!*$6!&+5,!0#9T/R-O&H1>BH!+)!x^]a!z<M!!_$6!&+5,!(+IP'&!564()+'(!C&6&!

$7)+-#&.!$#!),&!5$'.!*-#K&6!+#.!J(&.!*$6!+''!*J6),&6!5,+6+5)&6-V+)-$#M!!

,7`"N%827QP-aQ**NOP=S!!n(&.!<&@6H!/]Maa!K8!^HM>!II$'18!vT/R-O&H1>!/ZM[]!K8!H`M]!II$'1!

+#.!xHaa!I0!$*!NG_M!!U-&'.!HM]W!K!/WHMWk1M!!_N;SL!/v@68!5I;^1h!>`]Z/(18!^>]>/(18!

^^[W/(18!^a^>/I18!`HF/I18![WW`(18!Z]]/I18!FZ[/I8!(,18!F]Z/(18!Fa`/(1M!^H<e^Gf!TOL!

/^aaM]!OGV8!<Z?[1! >M][!9T/R-CGH1HBM!IP!^W`;^]H!l<M]8![F!

%B`"N%827QP-aQ**N-P=MS!!n(&.!RI<'H!/]Maa!K8!^`M]!II$'18!vT/R-O&H1>!/^^MF!K8!][MW!

II$'1!+#.!xHaa!I0!$*!NG_M!!U-&'.!FM]a!K!/]>M`k1M!!_N;SL!/v@68!5I;^1h!>`]W/(18!

>[`Z/I18!>WZH/C18!^>W[/(18!^^[[/(18!`[[/I18!`HZ/(18![>`/I18!ZFZ/I18!FZZ/(18!F][/(18!

FaH/(1M!!^H<e^Gf!TOL!/^aaM]!OGV8!<Z?[1! >M][!9T/R-CGH1HBM IP!^]W;^]`!z<M![F8![Z!

1@`"N%827QP-aQ**N-P=MT!!n(&.!?4<'H!/]Maa!K8!^[MF!II$'18!vT/R-O&H1>!/^^M^!K8!]]M`!

II$'1!+#.!xHaa!I0!$*!NG_M!!U-&'.!ZM[a!K!/][MFk1M!!_N;SL!/v@68!5I;^1h!>`][/(18!

>`aa/I18!>HF>/C18!^>Wa/(18!^^[Z/(18!`Z[/(18!`H`/(18![H>/I18!ZZ^/(18!Z]W`(8(,18!FZZ/I18!

F][/I18!FaF/(1M!^H<e^Gf!TOL!/^aaM]!OGV8!<Z?[1! >MFa!9T/R-CGH1HBM !IP!^F^;^F]!z<M!

*eW`"N%827QP-aQ*NRP=R!!n(&.!U7<'H!/]Maa!K8!^ZM`!II$'18!vT/R-O&H1>!/^aMZ!K8!]HM[!

II$'1!+#.!xHaa!I0!$*!NG_M!!U-&'.!HM]W!K!/HaMHk1M!!_N;SL!/v@68!5I;^1h!>`]`/(18!

^>][/(18!^^[Z`(18!`ZW/I18![HZ/I18![WF/I18!ZZH/I18!FZF/(18!F^a/(1M!!^H<e^Gf!TOL!

/^aaM]!OGV8!<Z?[1! >M]W!9T/R-CGH1HBM !IP!^FH;^F]!z<M![F8![Z!

/X`"N%827QP-aQ*NSP=M!!n(&.!0J<'H!/]Maa!K8!^ZM[!II$'18!vT/R-O&H1>!/^aMF!K8!]HMH!II$'1!

+#.!xHaa!I0!$*!NG_M!!U-&'.!]MFa!K!/W[M^k1M!!_N;SL!/v@68!5I;^1h!>`]]/(18!>HF>/C18!

^>]a/(18!^^[F/(18!`Z>/(18!`HF/(18![HH/I18!ZZF/(18!Z]W/(8!(,18!FF[/(18!F^Z/(1M!^H<e^Gf!

TOL!/^aaM]!OGV8!<Z?[1! >M]ZW!9T/R-CGH1HBM !IP!^FZ;^Za!z<M[F8![Z!!

3.2 Alkoxide Synthesis and Characterization

! "!K&#&6+'!(4#),&(-(!C-''!7&!.&(56-7&.8!(-#5&!),&!P6&P+6+)-$#!$*!+''!),&!0#/?@A1H!

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)6+#(*&66&.!)$!),&!>]!I0!%-+'!+#.!]!I0!$*!)$'J&#&!C+(!+..&.8!+#.!),&!I-3)J6&!C+(!

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%-+'!+#.!.-(($'%&.!-#!]!I0!)$'J&#&M!N,+)!($'J)-$#!C+(!+..&.!.6$P;C-(&!)$!),&!()-66-#K!

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)-I&!),&!6&+5)-$#!I-3)J6&!C+(!5$#5&#)6+)&.!74!('$C!&%+P$6+)-$#!$*!),&!%$'+)-'&!

5$IP$#&#)(!J#)-'!d;6+4!XJ+'-)4!564()+'(!C&6&!*$6I&.M!!

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3.3 Mixed Amide/Alkoxide Synthesis and Characterization

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3.4 CO2 Insertion Process and Characterization of Products

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3.5 Elevated Pressure of CO2 for Insertion into Ln(DBP)3

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3.7 General X-ray Crystal Structure Information

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4.1 Amides {Ln[N(SiMe3)2]3}

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1H_LuDBP

1H_CeDBP 1 1 C:\Bruker\TOPSPIN1.3 laottle

[ppm] 2.0 1.8 1.6 1.4 1.2 1.0

1H_LuDBP

1H_CeDBP 1 1 C:\Bruker\TOPSPIN1.3 laottle

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Vt_60_LuDBP_1H

Vt_60_LuDBP_1H 1 1 C:\Bruker\TOPSPIN1.3 laottle

[ppm] 2.0 1.5 1.0

Vt_60_LuDBP_1H

Vt_60_LuDBP_1H 1 1 C:\Bruker\TOPSPIN1.3 laottle

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5.1 Appendix A: TABLES

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