Page 13 of 14
Journal of the American Chemical Society
Vm'9LJ&AJ'gdYWhfcgWcdm'cZ'h\Y'`]ei]X&gc`]X']bhYfZUWY'cZ'J9F=Q'
!*,"''K\iU]%'D'4'9a]f]%'E''L'4'IiYghY``&KUbh]U[c%'Q''E'4'@Yfc[iY`%'
1
2
3
4
5
6
7
8
>'4'D]%'Q''<'4'C]a%'@'4'EY]`Ub%'J'4';\Udd`Y%';'4'JU`d\%'B'4'DihYf&
VUW\Yf%'B''K'%'>cfaU`XY\mXY'ghUV]`]nUh]cb'ZUW]`]hUhYg'`][b]b'acbc&
aYf'dfcXiWh]cb'Xif]b['V]caUgg'XYdc`maYf]nUh]cb''7;A=D;=#(&',"'
$&%%',+2&,,,''
!*-"''<Yigg%'H''B'4'KWchh%'E'4'LfUb%'>'4'OYghkccX%'F''B'4'XY'Nf]Yg%'B''
?'4':UfhU%'C'%'9fcaUh]W'EcbcaYfg'Vm']b'K]hi';cbjYfg]cb'cZ'JYUW&
h]jY'AbhYfaYX]UhYg']b'h\Y'9W]X&;UhU`mnYX'<Ydc`maYf]nUh]cb'cZ'D][&
b]b''1 #+C #-@=C #7E; #(&'+"'"$(%'0-./&0-/0''
!*."''OUb[%'E'4'R\Ub[%'P'';'4'D]%'@''B'4'Di%'B''E'4'D]i%'E''B'4'OUb[%'
>'%';UfVcb'EcX]Z]WUh]cb'cZ'F]W_Y`';UhU`mgh'Zcf'<Ydc`maYf]nUh]cb'
cZ'Gl]X]nYX'D][b]b'hc'9fcaUh]Wg''+-7#-9I9B #(&'."')%'*/*-&*/+)''
!*/"''R\Ub[%';''>'4'D]%'@''B'4'Di%'B''E'4'R\Ub[%'P'';'4'EUW9fh\if%'
C''='4'@Y[[Yb%'E'4'OUb[%'>'%'Hfcach]b['D][b]b'<Ydc`maYf]nUh]cb'
UbX'JYghfU]b]b['h\Y';cbXYbgUh]cb'j]U'Ub'Gl]XUh]cb&@mXfc[YbUh]cb'
KhfUhY[m''+-7#-9I9B #(&'-"'(%',-*2&,-+2''
!*0"''JU\]a]%'9'4'M`Vf]W\%'9'4';ccb%'B''B'4'KhU\`%'K''K'%'>cfa]W&UW]X&
]bXiWYX'XYdc`maYf]nUh]cb'cZ'cl]X]nYX'`][b]b'hc'UfcaUh]Wg''39IJG=#
(&'*"'&"&%'+-2&+.+''
!*1"''?UfYXYk%'E'4'Qcib[&>Uf\Uh%'<'4'BUW_gcb%'B''='4'KUZZfcb%';''
E'%'=`YWhfcWUhU`mh]W'Md[fUX]b['cZ'H\Ybc`]W';cadcibXg'GVgYfjYX'
UZhYf'D][b]b'Hmfc`mg]g''+-7#7JHI9AD9:B=#-@=C #.D? #(&'/"'(%'1,0.&
1,1/''
!*2"''KYf[YYj%'9''?'4'OYVV%'B''<'4'@Ufhk][%'B''>'%'9'@YhYfc[YbYcig'
F]W_Y`' ;UhU`mgh' Zcf' h\Y' @mXfc[Ybc`mg]g' cZ' 9fm`' =h\Yfg' k]h\cih'
9fYbY'@mXfc[YbUh]cb''1 #+C #-@=C #7E; #(&'("'"$%%'+)++/&+)++2''
!+)"''C`]b[Yf%'?''='4'R\ci%'Q''L'4'@Uc%'H'';'4'JcVV]bg%'B'4'9ei]`]bU%'
B''E'4'BUW_gcb%'B''='4'@Y[[%'=''D'%':]ca]aYh]W'JYXiWh]jY';`YUjU[Y'
cZ'CYhc'9fm`'=h\Yf':cbXg'Vm'KaU``&Ec`YWi`Y'L\]c`g''-@=C7JHK
-@=C%'(&'/%'"#%'-00.&-002''
!+*"''KYf[YYj%'9''?'4'@Ufhk][%'B''>'%'KY`YWh]jY%'F]W_Y`&;UhU`mnYX'
@mXfc[Ybc`mg]g'cZ'9fm`'=h\Yfg''7;A=D;=#(&''"'$$#%'-,2&--,''
!++"'';\Ub%'B''E''O'4':UiYf%'K'4'KcfY_%'@'4'KfYY_iaUf%'K'4'OUb[%'
C'4'LcghY%'>''<'%'KhiX]Yg'cb'h\Y'NUbUX]ia&;UhU`mnYX'Fcbcl]XUh]jY'
<Ydc`maYf]nUh]cb'cZ'E]gWUbh\ig'[][UbhYig&<Yf]jYX'D][b]b''+-7#
-9I9B #(&')"'$%'*,/2&*,00''
!+,"''F]W\c`g%'B''E'4':]g\cd%'D''E'4':Yf[aUb%'J''?'4'=``aUb%'B''9'%'
;UhU`mh]W';&G':cbX';`YUjU[Y'cZ'+&9fm`clm&*&Ufm`Yh\Ubc`g'UbX'Ahg'
9dd`]WUh]cb'hc'h\Y'<Ydc`maYf]nUh]cb'cZ'D][b]b&JY`UhYX'Hc`maYfg''
1 #+C #-@=C #7E; #(&'&"'"$#%'*+..-&*+...''
!+-"''@Y%'B''Q'4'R\Uc%';'4'DYfW\Yf%'B''9'%'F]&;UhU`mnYX';`YUjU[Y'cZ'
9fm`'=h\Yfg']b'h\Y'9eiYcig'H\UgY''1 #+C #-@=C #7E; #(&'("'"$%%'
+)0/1&+)00.''
!+."'':i`ih%'K'4'K]Ub_Yj]W\%'K'4'jUb'EimXYb%'9''H'4'9`YlUbXYf%'<''
L''D'4'KUjc[`]X]g%'?'4'R\Ub[%'B''?'4'@Uhn]aUb]_Uh]g%'N'4'QUb%'F'4'
<mgcb%'H''B'%'=ZZ]W]Ybh'W`YUjU[Y'cZ'Ufm`'Yh\Yf';&G'`]b_U[Yg'Vm'J\&
F]'UbX'Ji&F]'bUbcgWU`Y'WUhU`mghg'cdYfUh]b[']b'kUhYf''-@=C #7;A #
(&'."'*%'..,)&..,.''
!+/"'' E]hhYbXcfZYf%' >'4' @UZbYf%' B'%' @mXfc[YbUh]cb' cZ' VYbnYbY' cb'
F]!***"'&'U'<>L'ghiXm''1 #5@LH #-@=C #,#(&&("'"!'%'*,+22&*,,).''
!+0"''<Y``Y'K]hY%'D'4'9`Uj]%'9'4'9VfUag%';''>'%'9Xgcfdh]cb'YbYf[]Yg'
UbX'[YcaYhf]Yg'cZ'd\Ybc`'cb'h\Y'!***"'gifZUWY'cZ'b]W_Y`3'9b'UV']b&
]h]c'ghiXm''5@LH #6=K #,#(&&)"''(%',''
!+1"'';\]i%';'';'4'?YbYgh%'9'4':cf[bU%'9'4'JcgW\%'F'%'@mXfcXYclm&
[YbUh]cb'cZ'?iU]UWc`'cjYf'Ji!)))*"3'9'<>L'KhiXm''+-7#-9I9B #
(&'*"'%%'-*01&-*11''
!+2"''DYY%'C'4'?i%'?''@'4'Ei``Yb%';''9'4':cUhYb[%'9''9'4'N`UW\cg%'
<''?'%'?iU]UWc`'@mXfcXYclm[YbUh]cb'EYW\Ub]ga'cb'Hh!***"3'Ab&
g][\hg'Zfca'<Ybg]hm'>ibWh]cbU`'L\Ycfm'UbX'D]bYUf'>fYY'=bYf[m'JY&
`Uh]cbg''-@=C7JH-@=C#(&'+"')%',*.&,++''
!,)"''NUf[\YgY%'B''B'4'Eig\f]Z%'K''@'%'Gf][]bg'cZ'Wcad`Yl'gc`jYbh'
YZZYWhg'cb'W\Ya]WU`'fYUWh]j]hm'UbX'WcadihUh]cbU`'hcc`g'hc']bjYgh]&
[UhY'h\Ya3'U'fYj]Yk''6=9;I #-@=C #.D? #(&'/"'%%'*/.&+)/''
!,*"''XY';Ughfc%'A'':''<'4'?fUWU%'A'4'JcXf][iYn&?UfW]U%'D'4'CYbbYaU%'
E'4'J]bU`X]%'J'4'EYYa_Yb%'>'%'=`iW]XUh]b['h\Y'fYUWh]j]hm'cZ'aYh\&
clmd\Ybc`'dcg]h]cbU`']gcaYfg'hckUfXg'\mXfc[Yb&hfUbgZYf'fYUWh]cbg'
!J"'F]''-9I9B #7;A #8=;@DEB #(&'."')%',*)0&,**-''
!,+"'';\Yb%'E''E'4'EUYXU%'F'4':U]_Yf%'9'4'@iUb[%'B'%'Ec`YWi`Uf'
Abg][\h']bhc'Hh&;UhU`mnYX';\YacgY`YWh]jY'@mXfc[YbUh]cb'cZ'Ub'9f&
caUh]W'CYhcbY'Vm'Ab'K]hi'EcXi`Uh]cb&=lW]hUh]cb'AJ'KdYWhfcgWcdm''
+-7#-9I9B #(&'("'#%'+))0&+)*,''
!,,"'' B]Ub[%' K'4' ;\Yb%' R'4' ;\Yb%' P'4' F[imYb%' <'4' EUhhY]%' E'4'
?ciVYfh%'?'4'NUb'<imbY%'J''H'%'AbjYgh][Uh]cb'cZ';cVU`h'H\h\U`cWm&
Ub]bY' Uh' h\Y' Kc`]X(D]ei]X' AbhYfZUWY' Vm' =`YWhfcW\Ya]WU`' L]d&=b&
\UbWYX'JUaUb'KdYWhfcgWcdm''1 #5@LH #-@=C #-#(&'/"'"#$%'21.+&
21.2''
!,-"'':Y`ch%'?'4'<Yg^UfX]bg%'K'4'DYggUfX%'B'%'=`YWhfcWUhU`mh]W'@mXfc&
[YbUh]cb'cZ'Gf[Ub]W&;cadcibXg'cb'<YjUfXU';cddYf'UbX'JUbYm&
F]W_Y`' =`YWhfcXYg' ]b' :Ug]W&EYX]U'' 8=IG9@=<GED# 2=II # '/.*"' #&%'
.,-0&.,.)'''
!,."';mf%'9'4';\]`hn%'>'4'BYUbgcb%'H'4'EUfhY`%'9'4':fcggUfX%'D'4'DYg&
gUfX%'B'4'EYbUfX%'@'%'=`YWhfcWUhU`mh]W'\mXfc[YbUh]cb'cZ'`][b]b'acX&
Y`g'Uh'JUbYm'b]W_Y`'UbX'dU``UX]ia&VUgYX'Y`YWhfcXYg''-9D #1 #-@=C #
(&&&"'()%',)0&,*.'''
!,/"''DUa%';''@'4'DckY%';'':'4'D]%'R''D'4'Dcb[Y%'C''F'4'JUmVifb%'B''
L'4';U`XkY``%'E''9'4'@ciXY_%';''='4'EU[i]fY%'B'':'4'KUZZfcb%';''E'4'
E]``Yf%'<''B'4'BUW_gcb%'B''='%'=`YWhfcWUhU`mh]W'id[fUX]b['cZ'acXY`'
`][b]b' acbcaYfg' k]h\' YUfh\' UVibXUbh' aYhU`' Y`YWhfcXYg'' 0G==D#
-@=C #(&'+"'"(%'/)*&/)2''
!,0"' @Uc%' H'' =`YWhfcWUhU`mh]W' @mXfc[YbUh]cb' cZ' EcbcaYf]W%' <]&
aYf]W%' UbX' Hc`maYf]W' D][b]b' EcXY`' ;cadcibXg' k]h\' JUbYm'
F]W_Y`3' ;\Ya]ghfm%' EYW\Ub]gh]W%' UbX' HfcXiWh' Lcl]W]hm' KhiX]Yg''
H\'<''<]ggYfhUh]cb%'E]W\][Ub'KhUhY'Mb]jYfg]hm%'=Ugh'DUbg]b[%'EA%'
+)*1''
!,1"'':\U``U%'9'4':UbgU`%'F'4'Khc_`cgU%'J''B'4'>cibhU]b%'E'4'JU`d\%'
B'4'@cX[Y%'<'':'4'@Y[[%'=''D'%'=ZZYWh]jY'U`_U`]bY'aYhU`&WUhU`mnYX'
cl]XUh]jY' XY`][b]Z]WUh]cb' cZ' \mVf]X' dcd`Uf'' ,AEI=;@DEB # ,AE>J=BH #
(&',"'*%'*)''
!,2"''EU\XUj]%':'4'DUZfUbWY%'9'4'EUfhY`%'9'4'DYggUfX%'B'4'EYbUfX%'
@'4':fcggUfX%'D'%'=`YWhfcWUhU`mh]W'\mXfc[Ybc`mg]g'cZ'`][b]b'acXY`'
X]aYfg'Uh'JUbYm'b]W_Y`'Y`YWhfcXYg''1 #+FFB #.B=;IGE;@=C #'//-"'#(%'
/).&/**''
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
!-)"''9bXYfgYb%'E''D'4'EUh\]jUbUb%'F'4'OUmbYf%'<''<''E'%'=`YW&
hfcW\Ya]ghfm'cZ'Y`YWhfcb&hfUbgZYf'dfcVYg''L\Y'fc`Y'cZ'h\Y'`YUj]b['
[fcid']b'h\Y'W`YUjU[Y'cZ'fUX]WU`'Ub]cbg'cZ'U`d\U&Ufm`clmUWYhcd\Y&
bcbYg''1 #+C #-@=C #7E; #'//,"'"")%'-10*&-102''
!-*"'':UfVU%'>'4'NY`UgWc%'E''<'4'?i]fUXc%'9'%';Uh\cX]W'JYXiWh]cb'
cZ'H\YbUWm`':fca]XY''.B=;IGE;@AC #+;I9 #'/.)"'#)%'+.2&+/)''
!-+"'' FU_U\UfU%' C'4' FUVU%' C'4' KU]hc\%' L'4' Ki[U]%' L'4' GVUhU%' J'4'
F]g\]mUaU%'K'4'=]bU[U%'Q'4'QUaUachc%'L'%'=`YWhfcW\Ya]WU`'H]bUWc`'
;cid`]b[' cZ' 9WYhcd\YbcbY' Mg]b[' :cfcb&<cdYX' <]UacbX' =`YW&
hfcXY''-@=C.B=;IGE-@=C#(&'/"''%'-*.,&-*.0''
!-,"''EUif]Y``c%'>'4'HUcbY%'='4'H]YhfcdUc`c%'J'4':U`i%'9''E'4'DieiY%'
J'%';UhU`mh]W'LfUbgZYf'@mXfc[Ybc`mg]g'cZ'D][b]b&<Yf]jYX'9fcaUh]W'
=h\Yfg'HfcachYX'Vm':]aYhU``]W'HX(F]'KmghYag''+-7#7JHI9AD9:B=#
-@=C #.D? #(&'."''%'2+/2&2+0/''
!--"''JUX]WU`'VcbX'X]ggcW]Uh]cb'YbYf[]Yg'!:<=g%']b'_B(ac`"'Zcf'\c&
ac`mh]W';&G'W`YUjU[Y'kYfY'WcadihYX'Zcf'h\Y'`ckYgh'YbYf[m'Wcb&
ZcfaYfg'cZ'h\Y'fY`YjUbh'Yh\Yfg'Uh'h\Y'!:20P&N(/&,**$?!+XZ%+d"S/&
,**?!X"T((!:20P&<(/&,*?!X"'`YjY`'Zcf'WcadcibXg''%'(%'.%''&%''.%'
UbX''/''9g'YldYWhYX'Zcf'h\Y'YZZYWhg'cZ']bWfYUg]b['aYh\m`'giVgh]hi&
h]cb%' h\Y' :<=g' XYWfYUgY' ]b' h\Y' gYf]Yg''' !+/+'-"%' '/' !+.*'2"%' '&(
!+.)',"''K]a]`Uf`m%'Ug'YldYWhYX%'('!,*.')"%'.(!,)2'*"%'UbX''.(!,),'0"'
g\ck'XYWfYUg]b[':<=g''<Ygd]hY'h\Y]f'kYU_Yb]b['VcbXg%'h\YgY'giV&
ghfUhYgt'W`YUjU[Y'fUhYg'XYWfYUgY'U`cb['h\YgY'gYf]Yg'!gYY'>][''1U"'''
'
'
''
'
'
'
ACS Paragon Plus Environment