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The Trans Effect in Palladium Phosphine Sulfonate Complexes Elixabete Rezabal, Jesus M. M. Ugalde, and Gernot Frenking J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b06856 • Publication Date (Web): 19 Sep 2017 Downloaded from http://pubs.acs.org on September 30, 2017
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The Journal of Physical Chemistry A is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
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The Journal of Physical Chemistry
! " #$##% & ' " ! " $#() )##*# ' " +,+, -, , & ./ & 0&' 1 23#12 4" 5 ,4+ - 5 -" 6 5 1 )##$* ' "
' $1 )#$(
!" # $ % & #$%&!" ½
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σ
trans effect
3
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cis
trans
trans effect
!
trans
¾
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! "
# "
cis trans $ trans cis " cis trans "
% β & " cis trans & ' " β ( " "
) " cis trans * ( " σ π + trans ' " σ π +
π ' " ,
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The Journal of Physical Chemistry
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cis
π
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!
"
σ
π
=
#
$ %
$
σ
& &
≈
&
'( )* 8 '( + ,
- - * 'trans
influence *
'trans
/
effect *
trans
0 -
cis trans
trans influence
cis
trans
/
1
) .
- )
1
2
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The Journal of Physical Chemistry
! " # $ % % " & # $ " ' ( " ' % )"* +, # $ % "
, "
- #' "' & .$ / 0- e Δ-prep Δ-int −De ≡ ΔE = ΔEprep + ΔEint .
, , , 1
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ΔEint = ΔESteric + ΔEoi
ΔESteric = ΔEelst + ΔEP auli
Δelst
ΔP auli
! " #
$ %
Δoi
! #
$
ΔSteric
%
!
& ' ( )* + ζ %, +-. % $ %' ! /012 !
Δoi
3 4
Δρ(r)
!
*
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influence
trans
!
" #
$
%
&
' cis trans (
) (
* ! π & σ + , ! σ π " π
* + , σ
% &- cis trans !
.!/ !0 3 ./ 12342 53 ( 1 − 4 0 *1,
1
6
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trans cis → trans Δ
!
" cis → trans ΔG ΔE # cis − trans $ %3 & & & ' ( %3 & & & ' ΔEint
ΔEint
Δ Δ Δ Δ trans cis Δ trans cis Δ ΔΔ ! ! " ! cis #$ $ !$$ ! ! trans #$ 3
) * $ * # cis
trans
+ %3 & & * trans * # ! ,, ( - cis * & ' + # $ # ( . %3 & & ΔEint # /0 , 1,
2,,
# cis trans 3 & ' trans # 4 21
* cis
%3 & &
& ' * → trans
#
5 # ΔG ΔE
# + #
!
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ΔE cis trans ΔG ΔG cis − trans ΔE cis − trans trans cis
ΔEint ΔESteric ΔEoi ! "# !$%% $ cis trans ΔE &&'3 &( ΔEint &&'3 trans ) cis ΔEint &( cis &( trans cis − trans ΔEint *+ ! % , -. ! % /0 1 cis trans ΔEint &&'3 &( ΔEint &&'3 .$ ! % -$$ ! % /0 &( trans ) &&'3 cis −trans ΔE ΔEint &&'3 &( ΔΔEint 2 2 2 ΔE ( &'3 3 .
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trans
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ΔEint
ΔEP auli
ΔEelst
ΔEoi
ΔESteric
!"
ΔEoi
# $
%
&
'
Ñ¿
trans
+ ,
ѽ
+ ,
trans
trans influence
cis
ΔEoi
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/0
cis
trans
#))
( 3 & .&
&.
ѽ
1
+
-
ΔESteric
#$)
&.
& ( 3 $*)
ΔEoi
trans influence
cis
21-3 % # 4
ΔEoi !%&21-3 &
5 $
#
!%&21-3
67
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ΔESteric ΔEoi !" #$ " % % & $ ΔESteric ΔEoi " trans ' $ ()$* +$, $ *$ */$/ ()$+ /$/ /$, -.3 " $0 */$) +$* /$ cis ' $+ ($ /$0 "$/ "$ -.3 trans ' ,$( +$+ 0$/ "$* 0$ ,)$" ("$, *$+ *$* -.3 $* ($/ *$ *$* "$" cis ' /$ ( $* ($+ ($ "$* -.3 trans ' 0$( $ )$+ "$ 0$" ,0$ (*$" 0$( ,$+ -.3 $ " $) /$0 /$" "$( cis ' "$ ()$0 ($, ($) "$/ -.3 trans ' $( ")$" ($/ ($" ($, ($, ,"$+ (($0 ,$/ ,$ -.3 $/ (0$, $, 0$* )$ cis ' ($( ($" *$* "$, "$" -.3 1 2 && 1 . 3$
4& % 5 - -.3 2 1 1 5 6 1 7 & 5 # "3$ 8 7 # " 3
& σ % - 9 & x −y % -$ % trans 7 5 (*$" ()$+ 3 % cis &4 7+$* 7 3 ($, 7 3 3$ 5 8 && π % yz xy % 2 π % -.3 7 & 21 " % # "3$ 2
2
-' 6 & 1& % π 1& 7m1 − 3 − 43 σ 1& 7m2 − 43 % '
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trans
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cis trans) m1 π ΔEoi ∼ !
cis
" trans
trans
#
$ % cis &' ! (
π )*) z 2 # + !
cis
xy π ∗ )*) trans $ $ , 3 $ cis , 3 $ - # σ ./ 0 σ π 0 . cis trans m2 − 4$ # σ "" 1 σ $ x2 −y2 trans z 2 cis
# ( 0 .$ # → . → π trans " " cis %
σ
σ $ , 3 x2 −y2 trans .
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cis
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z 2 3 x2 −y 2
zx
trans
zy
cis
xy
3
cis → trans
trans
! "
3
# # # #
Δ
σ
trans influence
$ % #
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σ
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()
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c1 − 4
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π
σ
+
-)
%
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& ' %
*
π
#
%/ , .0$
1( 2 '
π
π
trans
#
/-
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Trans
!
!" #
!π
!π
!$$ % &
!$'( % &
#
!$)* % &
+
!"
trans !$, % &
πtrans -!$*&!$*$
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% &
!"
' cis → trans # ΔG ΔE % &
. / !" ΔEint % &
cis trans
σ π σ π
ΔG
!$)0 !$() !$,1 !$$ !$'$ !$'(
ΔE
!$)0 !$'* !((0 !$( !$'$ !$'2
Δ
! )$* )$1 )($ )$, )$, )$,
Δ
!" !)$' !)$) !)), !)$2 !)$' !)$'
$2
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ΔEint trans cis
!()$ !((( !$1( !$* !$1) !$*$
!''' !(** !$,1 !')0 !(1) !(,1
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π cis
cis
trans influence ! " " # trans # ! " $ # % & ' '
! !! (
%! $ # " cis trans % #
' $ cis & trans π # ) π π &'* ! ! # !# '
$ # σ
)++ , σ σ &'* % ( # π σ #
- ' . & &' cis → trans / ' ) # * " $ #
' trans cis σ σ # & & !
σ' ' ' σ cis − trans / 0## ' Δ0 ! σ #' # ' ' 1 &' #
' ' , # trans cis 2 $ #
' #! # ΔEoi ) %# 3* ' ! '
% # ' ΔEoi c4 − 2 − 3 $ σ c4 − 3 − 1 $ π ( # - cis ' trans
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ΔESteric ΔEoi !" #$ " % % & % #$ $ ΔSteric Δoi ' " trans ' $' $" ($) "$( "'$' )*$* "+$' '*$' cis ,$* "+$, ($+ "$* trans $ '$ '*$- )$* "$ cis $* ''$- "$ σ trans -$ '-$' -$' $+ σ cis ''$, +$' )$( "$( π trans ",$) )($' "'$) ' $ π cis $* '($- *$- $) $" σ trans '+$" ,$" ''$* +$ ,$' σ cis '*$' '$" )$ )$, π trans '$) -'$ ",$ ' $ π cis . & % / cis & 0 % π 1& &2 3 trans σ 1& &2 / 0 $ . 3 ΔEoi / 1 1 % π σ &2 & 1 π &2 4 ΔESteric / 3 51 σπ & trans &2 $
1 1 / & % &2 6 && 1 7 % 1 % "$ $ 1 σ % % σ 1& $ σ % 0 & cis & $ 3 1 1 &1 c2 %3 1 1 c4 1 1 c3$ 8 π 3 1 1 cis &2 $ -
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π
πtrans/cis
σ
c1
trans
c3
c4
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c3
c4
π
c1
cis
−!"#2 $−"−
!
#3 %
%
&
' %
trans
trans influence
' %
(3
)
trans effect
!# !
#
* % (3
trans
σ
+,
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3
trans 3
! " # 3 cis
cis
! #
! 3
trans #
! trans σ
3
trans cis
trans effect $ trans
% cis 3
# &
% cis 3
'
# ! (
!
σ -
%
π
π % ) * +, π % ! ./
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π %
The Journal of Physical Chemistry
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π
π
σ Δ ! "
# $Δ% " & #' ( ) * σ
$
Δ
+ , # $Δ% " + #''
- . π
$ + ' * *
π → π
.
* ) - ) σ → σ → π
/
σ
σ
) )
. * π - ))
π → π
. 0
π *
* trans influence σ 1 trans influence
2 ) 3 4$55'
5 ) 6
σ
7 . ) Δ int $ '
$ '
$ ' * 8
,
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! " # $ % $ & $ '()*+ ' + ' #,- .''// ,-% 01! +! 2 * 2 2 $ &
( 22 3 + ( 2 23 ( 4 3 % 0 !& $ 0 #$ # * # . 2 6 !5 3 + & 5567*5589&
/ 1&3 % 0 !& : " . ; )2$ # $ # *+ * 1 # " :2 & 75886&
" $ $ .&%&3 ,2 +2? '&3 02 " $ ; $ ; -) $ & @9A7>11 ?
4 . @ + 3 ?A /'
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"
4 ; /!
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'5 B - . . - 3 C :2
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! " ! # !" ! $$" %&' (! )*" +& ,' +" $ - " ." - *" +'* (/ / $ 0))1 $!$! / $ 234 +!5 " 6 ! 7 8 / $!$! / $ 0))1 $ 9 2224
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D* 7 " ! ! ! . / $ $ > $ > / , ? * / "# "# $ @3
D* 7 . E* . / , "# "# C3 C34
;! A" ! B % F9$ * ! - / / ! % . ,.
+ B 7 / + % $ ! ! G H ) % & C 2@ C 4
2
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! " # $ !% &'()&*+
, ! - - " &(&*)&.(*
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3$ 3 % #0 / " 0 # 0 " 22..
4 " 5 ! ! # 0 #" "/ $ 6(78 6(78 6(78 "618 "6.78 # 9 " (::2(:*:
4 " 5 ! "/ "; " 3 ! 4 " ! " # % " " 0 !# &*.&+:
= > 3 ! ? 0 " 0 " " "/ '@+)'::
! = > 3 4 " - 0" " # (&'')(&'& .:
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! !
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