Isolation and structural characterization of a titanacyclopropane as key intermediate in the double aryl Grignard addition to 2-(arylethynyl)pyridine derivatives

Article abstract of DOI:10.1039/c8cc00478a

A titanacyclopropane species, which is a key reaction intermediate in the Ti(OiPr)₄-mediated double aryl Grignard addition to 1,2-di(pyridin-2-yl)ethyne and related alkynes, was isolated and fully characterized. Based on this observation a one-pot synthesis of diarylated 1,2-di(pyridin-2-yl)ethanes and 2-(1,2,2-triarylvinyl)-pyridines was developed, including the tetraarylation of V-shaped 2,6-bis(arylethynyl)pyridines.

Full text of DOI:10.1039/c8cc00478a

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0.1039/C8CC00478A.
Volume 52 Number
1
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January 2016 Pages 1–216
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COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
N@D5h-C80
rsc.li/chemcomm

ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ
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DOI: 10.1039/C8CC00478A
Wꢀꢁꢂꢃꢄꢅ bꢄꢆꢇ
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ꢁꢂꢂꢃꢄꢅꢀꢆꢇꢅꢁꢄꢈ
Lꢌꢀꢅꢄꢐꢑꢀꢃ ꢄꢃꢒ {ꢐꢂꢁꢍꢐꢁꢂꢄꢅ /ꢓꢄꢂꢄꢍꢐꢇꢂꢑꢔꢄꢐꢑꢀꢃ ꢀꢕ ꢄ Çꢑꢐꢄꢃꢄꢍꢖꢍꢅꢀꢗꢂꢀꢗꢄꢃꢇ
ꢄꢌ Yꢇꢖ Lꢃꢐꢇꢂꢆꢇꢒꢑꢄꢐꢇ ꢑꢃ ꢐꢓꢇ 5ꢀꢁ"ꢅꢇ !ꢂꢖꢅ Dꢂꢑꢎꢃꢄꢂꢒ !ꢒꢒꢑꢐꢑꢀꢃ ꢐꢀ %&
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ꢆꢘꢘꢔꢩꢙꢔꢦꢈꢝꢝꢙꢉꢈꢴꢑꢐꢎꢑꢏꢖꢈꢜꢝꢞꢞꢈ
'
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ꢑ
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ꢑ
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ꢲꢁꢅꢯꢈꢡꢝꢟꢡꢝꢢꢳ/ꢞꢝꢞꢞꢝꢝꢝꢝꢝꢞꢈ
FꢏꢑꢐꢘꢔꢋꢘꢍꢈFꢍꢋꢘꢉꢊꢠ ꢈꢇꢍꢏꢋꢙꢔꢐꢈꢕꢍꢙꢉꢠ ꢈꢂꢑꢏꢵꢎꢋꢈꢪꢐꢦꢔꢏꢋꢠ ꢈꢶꢎꢮꢔꢏꢙꢈꢷꢑꢦꢔꢩꢍꢉꢒꢠ ꢈꢪꢏꢊꢘꢈꢀꢒꢍꢙ ꢈꢈ
ꢑꢠ
ꢊꢊꢊꢋꢂꢌꢍꢋꢀꢂꢎꢏ
ꢑꢐꢦꢈꢸꢎꢙꢹꢈꢶꢟꢈꢺꢑꢦꢔ ꢻꢈ
!
ꢐꢑꢐꢄꢃꢄꢍꢖꢍꢅꢀꢗꢂꢀꢗꢄꢃꢇ ꢌꢗꢇꢍꢑꢇꢌ* ꢊꢓꢑꢍꢓ ꢑꢌ ꢄ +ꢇꢖ ꢂꢇꢄꢍꢐꢑꢀꢃ ꢑꢃꢐꢇꢂꢆꢇꢒꢑꢄꢐꢇ ꢊꢐꢙꢔꢏꢛꢔꢦꢊꢑꢙꢔꢠꢈꢧꢔꢐꢔꢏꢑꢙꢔꢦꢈꢊꢐꢈꢑꢈꢛꢎꢒꢙꢊꢋꢙꢔꢩꢈꢏꢔꢑꢘꢙꢊꢍꢐꢈꢋꢔꣅꢎꢔꢐꢘꢔꢠꢈꢉꢑꢋꢈꢮꢔꢔꢐꢈ
ꢑꢃ ꢐꢓꢇ Çꢑ'hꢀtꢂ( &ꢆꢇꢒꢑꢄꢐꢇꢒ ꢒꢀꢁ"ꢅꢇ ꢄꢂꢖꢅ Dꢂꢑꢎꢃꢄꢂꢒ ꢄꢒꢒꢑꢐꢑꢀꢃ ꢐꢀ ꢉ*%& ꢩꢍꢋꢙꢎꢒꢑꢙꢔꢦꢈꢮꢑꢋꢔꢦꢈꢍꢐꢈꢊꢋꢍꢒꢑꢙꢔꢦꢈꢑꢐꢦꢈꢘꢉꢑꢏꢑꢘꢙꢔꢏꢊꢹꢔꢦꢈꢊꢐꢙꢔꢏꢛꢔꢦꢊꢑꢙꢔꢋꢈꢑꢐꢦꢈ
.
ꢒꢑ'ꢗꢖꢂꢑꢒꢑꢃ&%&ꢖꢅ(ꢇꢐꢓꢖꢃꢇ ꢄꢃꢒ ꢂꢇꢅꢄꢐꢇꢒ ꢄꢅ+ꢖꢃꢇꢌ* ꢊꢄꢌ ꢑꢌꢀꢅꢄꢐꢇꢒ ꢄꢃꢒ ꢕꢁꢅꢅꢖ ꢋꢖꢋꢙꢔꢛꢑꢙꢊꢘꢈꢲFꢇꢈꢛꢍꢦꢔꢒꢊꢐꢧꢈꢍꢚꢈꢙꢉꢔꢈꢏꢔꢑꢘꢙꢊꢭꢊꢙꢖꢈꢍꢚꢈꢙꢉꢔꢈꢊꢐꢈꢋꢊꢙꢎꢈꢧꢔꢐꢔꢏꢑꢙꢔꢦꢈ
ꢍꢓꢄꢂꢄꢍꢐꢇꢂꢑꢔꢇꢒꢋ ꢘꢄꢌꢇꢒ ꢀꢃ ꢐꢓꢑꢌ ꢀ"ꢌꢇꢂ)ꢄꢐꢑꢀꢃ ꢄ ꢀꢃꢇ&ꢗꢀꢐ ꢌꢖꢃꢐꢓꢇꢌꢑꢌ ꢀꢕ ꢋꢩꢔꢘꢊꢔꢋꢟꢈ
ꢒꢑꢄꢂꢖꢅꢄꢐꢇꢒ ꢉ*%&ꢒꢑ'ꢗꢖꢂꢑꢒꢑꢃ&%&ꢖꢅ(ꢇꢐꢓꢄꢃꢇꢌ ꢄꢃꢒ %&'ꢉ*%*%&ꢐꢂꢑꢄꢂꢖꢅ)ꢑꢃꢖꢅ(&
Previous work (ref 4):
X
ꢗꢖꢂꢑꢒꢑꢃꢇꢌ ꢊꢄꢌ ꢒꢇ)ꢇꢅꢀꢗꢇꢒ* ꢑꢃꢍꢅꢁꢒꢑꢃꢎ ꢐꢓꢇ ꢐꢇꢐꢂꢄꢄꢂꢖꢅꢄꢐꢑꢀꢃ ꢀꢕ ë&ꢌꢓꢄꢗꢇꢒ
*1&"ꢑꢌ'ꢄꢂꢖꢅꢇꢐꢓꢖꢃꢖꢅ(ꢗꢖꢂꢑꢒꢑꢃꢇꢌꢋ
Mg
R
Ar
N
O
%
Ar
Ar
N
N
HN
exc. ArMgBr
Ti(OiPr)4
TiL
H+
N
H
Ar
n
ꢅꢐꢈ ꢋꢊꢙꢎꢈ ꢧꢔꢐꢔꢏꢑꢙꢔꢦꢈ ꢮꢊꢋꢫꢑꢒꢵꢍꢞꢖꢬꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢋꢈ ꢧꢔꢐꢔꢏꢑꢙꢔꢦꢈ ꢮꢖꢈ
ꢏꢔꢑꢘꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢇꢊꢫꢅꢼꢬꢈ ꢑꢒꢵꢍꢞꢊꢦꢔꢋꢈ ꢑꢐꢦꢈ ꢑꢒꢊꢩꢉꢑꢙꢊꢘꢈ ꢺꢏꢊꢧꢐꢑꢏꢦꢈ ꢏꢔꢑꢧꢔꢐꢙꢋꢈ ꢉꢑꢭꢔꢈ
ꢧꢊꢭꢔꢐꢈ ꢏꢊꢋꢔꢈ ꢙꢍꢈ ꢑꢈ ꢒꢑꢏꢧꢔꢈ ꢭꢑꢏꢊꢔꢙꢖꢈ ꢍꢚꢈ ꢙꢊꢙꢑꢐꢊꢎꢛꢈ ꢛꢔꢦꢊꢑꢙꢔꢦꢈ ꢍꢏꢧꢑꢐꢍꢛꢔꢙꢑꢒꢒꢊꢘꢈ
ꢏꢔꢑꢘꢙꢊꢍꢐꢋꢟꢈꢅꢙꢈꢉꢑꢋꢈꢮꢔꢔꢐꢈꢙꢉꢔꢈꢩꢊꢍꢐꢔꢔꢏꢊꢐꢧꢈꢽꢍꢏꢵꢈꢮꢖꢈꢾꢎꢒꢊꢐꢵꢍꢭꢊꢘꢉꢈꢑꢐꢦꢈꢗꢑꢙꢍꢈ
N
This work:
H
ꢽ
ꢉꢊꢘꢉꢈꢉꢑꢋꢈꢔꢋꢙꢑꢮꢒꢊꢋꢉꢔꢦꢈ ꢙꢉꢔꢈꢋꢖꢐꢙꢉꢔꢙꢊꢘꢈ ꢩꢍꢙꢔꢐꢙꢊꢑꢒꢈꢍꢚꢈꢛꢊꢐꢊꢛꢑꢒꢒꢖꢈꢒꢊꢧꢑꢙꢔꢦꢈ
Py
Py
Ar
H
N
N
Ar
Ar
ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ ꢋꢩꢔꢘꢊꢔꢋꢟꢈ ꢕꢔꢑꢘꢙꢊꢍꢐꢈ ꢩꢑꢙꢙꢔꢏꢐꢋꢈ ꢏꢑꢐꢧꢔꢈ ꢚꢏꢍꢛꢈ ꢙꢉꢔꢈ
ꢡꢠꢜꢣꢊꢐꢋꢔꢏꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢔꢋꢙꢔꢏꢋꢠꢈ ꢑꢛꢊꢦꢔꢋꢈ ꢑꢐꢦꢈ ꢐꢊꢙꢏꢊꢒꢔꢋꢈ ꢊꢐꢙꢍꢈ ꢙꢉꢔꢈ
H+
exc. ArMgBr
N
TiL
m
Ar
ꢡ
Ti(OiPr)
4
ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈꢏꢊꢐꢧ ꢈꢙꢍꢈꢙꢉꢔꢈꢋꢖꢐꢙꢉꢔꢋꢊꢋꢈꢍꢚꢈꢑꢒꢒꢖꢒꢊꢘ/ꢑꢒꢒꢔꢐꢖꢒꢊꢘꢈꢙꢊꢙꢑꢐꢊꢎꢛꢈ
N
ꢜ
ꢏꢔꢑꢧꢔꢐꢙꢋꢠ ꢈ ꢊꢐꢙꢏꢑꢛꢍꢒꢔꢘꢎꢒꢑꢏꢈ ꢐꢎꢘꢒꢔꢍꢩꢉꢊꢒꢊꢘꢈ ꢑꢘꢖꢒꢈ ꢋꢎꢮꢋꢙꢊꢙꢎꢙꢊꢍꢐꢈ ꢫꢅꢄꢆꢗꢬꢈ
Py = 2-pyridyl
ꢢ
ꢿ
ꢏꢔꢑꢘꢙꢊꢍꢐꢋꢠ ꢈ ꢦꢊꢭꢔꢏꢋꢔꢈ ꢘꢍꢎꢩꢒꢊꢐꢧꢋꢈ ꢍꢚꢈ ꢑꢒꢵꢖꢐꢔꢋꢈ ꢑꢐꢦꢈ ꢑꢒꢵꢔꢐꢔꢋ ꢈ ꢑꢋꢈ ꢽꢔꢒꢒꢈ ꢑꢋꢈ
ꢡꢣꣀ
ꢿ
ꢏꢔꢒꢑꢙꢔꢦꢈ ꢙꢏꢑꢐꢋꢚꢍꢏꢛꢑꢙꢊꢍꢐꢋꢟ ꢈ ꢗꢊꢐꢘꢔꢈ ꢇꢊꢫꢁꢈꢥꢏꢬꢿꢈ ꢑꢐꢦꢈ ꢛꢑꢐꢖꢈ ꢺꢏꢊꢧꢐꢑꢏꢦꢈ {ꢍꢓꢇꢆꢇ ꢉ ꢇꢊꢫꢁꢈꢥꢏꢬ ꢣꢛꢔꢦꢊꢑꢙꢔꢦꢈꢦꢍꢎꢮꢒꢔꢈꢑꢏꢖꢒꢑꢙꢊꢍꢐꢈꢍꢚꢈꢜꢣꢘꢖꢑꢐꢍꢩꢖꢏꢊꢦꢊꢐꢔꢈꢫꢙꢍꢩꢬꢈꢑꢐꢦꢈ
ꢡꢠꢜꢣꢦꢊꢫꢩꢖꢏꢊꢦꢊꢐꢣꢜꢣꢖꢒꢬꢔꢙꢉꢑꢐꢔꢈ ꢫꢮꢍꢙꢙꢍꢛꢬꢈ ꢐꢈꢁꢈ ꢚꢍꢏꢛꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢑꢹꢑꢙꢊꢙꢑꢐꢑꢣꢈ ꢑꢐꢦꢈ
ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈꢋꢩꢔꢘꢊꢔꢋꢠꢈꢏꢔꢋꢩꢔꢘꢙꢊꢭꢔꢒꢖꢟ
ꢏꢔꢑꢧꢔꢐꢙꢋꢈ ꢑꢏꢔꢈ ꢑꢭꢑꢊꢒꢑꢮꢒꢔꢈ ꢊꢐꢈ ꢮꢎꢒꢵꢈ ꢑꢙꢈ ꢒꢍꢽꢈ ꢩꢏꢊꢘꢔꢠꢈ ꢙꢉꢔꢈ ꢛꢎꢒꢙꢊꢘꢍꢛꢩꢍꢐꢔꢐꢙꢈ
ꢏꢔꢑꢘꢙꢊꢍꢐꢋꢈ ꢮꢑꢋꢔꢦꢈ ꢍꢐꢈ ꢙꢉꢊꢋꢈ ꢑꢩꢩꢏꢍꢑꢘꢉꢈ ꢩꢏꢍꢭꢊꢦꢔꢈ ꢑꢐꢈ ꢑꢙꢙꢏꢑꢘꢙꢊꢭꢔꢈ ꢏꢍꢎꢙꢔꢈ ꢙꢍꢈ
ꢉꢊꢧꢉꢒꢖꢈꢚꢎꢐꢘꢙꢊꢍꢐꢑꢒꢊꢹꢔꢦꢈꢋꢖꢐꢙꢉꢔꢙꢊꢘꢈꢙꢑꢏꢧꢔꢙꢋꢟꢈꢈ
ꢈ
ꢇꢉꢔꢈ ꢍꢮꢋꢔꢏꢭꢔꢦꢈ ꢘꢑꢏꢮꢍꢣꢈ ꢑꢐꢦꢈ ꢑꢹꢑꢩꢉꢊꢒꢊꢘꢈ ꢺꢏꢊꢧꢐꢑꢏꢦꢈ ꢑꢦꢦꢊꢙꢊꢍꢐꢈ ꢙꢍꢈ ꢙꢉꢔꢈ
ꢐꢊꢙꢏꢊꢒꢔꢈꢧꢏꢍꢎꢩꢈꢊꢐꢋꢩꢊꢏꢔꢦꢈꢎꢋꢈꢙꢍꢈꢔꢞꢙꢔꢐꢦꢈꢙꢉꢔꢈꢦꢍꢎꢮꢒꢔꢈꢑꢏꢖꢒꢑꢙꢊꢍꢐꢈꢙꢍꢈꢏꢔꢒꢑꢙꢔꢦꢈ
≡ꢀꢈ ꢙꢏꢊꢩꢒꢔꢈ ꢮꢍꢐꢦꢔꢦꢈ ꢋꢎꢮꢋꢙꢏꢑꢙꢔꢋꢟꢈ ꢇꢉꢊꢋꢈ ꢐꢍꢙꢈ ꢍꢐꢒꢖꢈ ꢩꢏꢍꢭꢊꢦꢔꢦꢈ ꢙꢉꢔꢈ
ꢈ
ꢅꢐꢈ ꢙꢉꢔꢈ ꢘꢑꢋꢔꢈ ꢍꢚꢈ ꢗꢑꢙꢍꣁꢋꢈ ꢏꢔꢑꢧꢔꢐꢙꢈ ꢙꢉꢔꢈ ꢊꢐꢈ ꢋꢊꢙꢎꢈ ꢧꢔꢐꢔꢏꢑꢙꢔꢦꢈ
ꢅꢅ
ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ ꢑꢘꢙꢋꢈ ꢑꢋꢈ ꢑꢈ ꢇꢊ ꢈ ꢋꢖꢐꢙꢉꢍꢐꢈ ꢊꢐꢈ ꢏꢔꢑꢘꢙꢊꢍꢐꢋꢈ ꢽꢊꢙꢉꢈ
ꢚꢎꢐꢘꢙꢊꢍꢐꢑꢒꢊꢹꢔꢦꢈ ꢑꢒꢵꢖꢐꢔꢋꢠꢈ ꢑꢘꢙꢊꢭꢑꢙꢊꢐꢧꢈ ꢙꢉꢔꢛꢈ ꢙꢍꢽꢑꢏꢦꢋꢈ ꢑꢙꢙꢑꢘꢵꢈ ꢮꢖꢈ
ꢔꢒꢔꢘꢙꢏꢍꢩꢉꢊꢒꢔꢋꢟꢈ ꢀꢍꢐꢭꢔꢏꢋꢔꢒꢖꢠꢈ ꢐꢎꢘꢒꢔꢍꢩꢉꢊꢒꢊꢘꢈ ꢑꢙꢙꢑꢘꢵꢈ ꢍꢚꢈ ꢀ≡ꣂ/ꢀ≡ꢀꢈ ꢙꢏꢊꢩꢒꢔꢈ
ꢮꢍꢐꢦꢔꢦꢈ ꢋꢎꢮꢋꢙꢏꢑꢙꢔꢋꢠꢈ ꢽꢉꢊꢘꢉꢈ ꢑꢏꢔꢈ ꢑꢩꢩꢏꢍꢩꢏꢊꢑꢙꢔꢒꢖꢈ ꣃꢑꢐꢘꢉꢍꢏꢔꢦꣃꢈ ꢙꢍꢈ ꢑꢈ ꢇꢊ ꢈ
ꢘꢔꢐꢙꢏꢔꢈ ꢋꢉꢍꢎꢒꢦꢈ ꢮꢔꢈ ꢔꢐꢉꢑꢐꢘꢔꢦꢟꢈ ꢷꢔꢈ ꢏꢔꢘꢔꢐꢙꢒꢖꢈ ꢦꢔꢭꢔꢒꢍꢩꢔꢦꢈ ꢇꢊꢫꢁꢈꢥꢏꢬꢿꢣ
ꢛꢔꢦꢊꢑꢙꢔꢦꢈꢘꢑꢏꢮꢍꢣꢈꢑꢐꢦꢈꢑꢹꢑꢩꢉꢊꢒꢊꢘꢈꢦꢍꢎꢮꢒꢔꢈꢑꢏꢖꢒꢈꢺꢏꢊꢧꢐꢑꢏꢦꢈꢑꢦꢦꢊꢙꢊꢍꢐꢈꢙꢍꢈꢜꢣ
ꢀ
ꢍꢩꢩꢍꢏꢙꢎꢐꢊꢙꢖꢈꢙꢍꢈꢍꢮꢙꢑꢊꢐꢈꢑꢦꢦꢊꢙꢊꢍꢐꢑꢒꢈꢊꢐꢋꢊꢧꢉꢙꢈꢊꢐꢙꢍꢈꢙꢉꢔꢈꢛꢎꢒꢙꢊꢋꢙꢔꢩꢈꢏꢔꢑꢘꢙꢊꢍꢐꢈ
ꢅꢼ ꢛꢔꢘꢉꢑꢐꢊꢋꢛꢋꢈ ꢍꢚꢈ ꢋꢎꢘꢉꢈ ꢙꢏꢑꢐꢋꢚꢍꢏꢛꢑꢙꢊꢍꢐꢋꢈ ꢮꢎꢙꢈ ꢛꢊꢧꢉꢙꢈ ꢑꢒꢋꢍꢈ ꢒꢔꢑꢦꢈ ꢙꢍꢈ
ꢋꢙꢎꢘꢙꢎꢏꢑꢒꢈ ꢔꢭꢊꢦꢔꢐꢘꢔꢈ ꢚꢍꢏꢈ ꢙꢉꢔꢈ ꢵꢔꢖꢈ ꢏꢔꢑꢘꢙꢊꢭꢔꢈ ꢊꢐꢙꢔꢏꢛꢔꢦꢊꢑꢙꢔꢋꢈ ꢊꢐꢭꢍꢒꢭꢔꢦꢟꢈ ꢅꢐꢈ
ꢙꢉꢊꢋꢈꢽꢍꢏꢵꢈꢽꢔꢈꢋꢉꢍꢽꢈꢙꢉꢑꢙꢈꢦꢍꢎꢮꢒꢔꢈꢑꢦꢦꢊꢙꢊꢍꢐꢈꢙꢍꢈꢜꢣꢑꢒꢵꢖꢐꢖꢒꢩꢖꢏꢊꢦꢊꢐꢔꢈꢙꢏꢊꢩꢒꢔꢈ
ꢮꢍꢐꢦꢋꢈ ꢧꢊꢭꢔꢋꢈ ꢏꢊꢋꢔꢈ ꢙꢍꢈ ꢙꢉꢔꢈ ꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢊꢐꢧꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ ꢋꢩꢔꢘꢊꢔꢋꢈ
ꢚꢍꢏꢈ ꢽꢉꢊꢘꢉꢈ ꢍꢐꢔꢈ ꢦꢔꢏꢊꢭꢑꢙꢊꢭꢔꢈ ꢘꢍꢎꢒꢦꢈ ꢮꢔꢈ ꢊꢋꢍꢒꢑꢙꢔꢦꢈ ꢑꢐꢦꢈ ꢘꢍꢛꢩꢒꢔꢙꢔꢒꢖꢈ
ꢋꢙꢏꢎꢘꢙꢎꢏꢑꢒꢒꢖꢈ ꢘꢉꢑꢏꢑꢘꢙꢔꢏꢊꢹꢔꢦꢟꢈ ꢥꢏꢍꢙꢍꢐꢍꢒꢖꢋꢊꢋꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ
ꢦꢊꢑꢋꢙꢔꢏꢔꢍꢋꢔꢒꢔꢘꢙꢊꢭꢔꢒꢖꢈ ꢖꢊꢔꢒꢦꢔꢦꢈ ꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢙꢔꢦꢈ ꢑꢒꢵꢑꢐꢔꢋꢈ ꢫꢗꢘꢉꢔꢛꢔꢈ ꢡꢠꢈ
ꢮꢍꢙꢙꢍꢛ꣆ꢈꢗꢘꢉꢔꢛꢔꢈꢜꢬꢟꢈ
꣄
ꢩꢖꢏꢊꢦꢊꢐꢔꢘꢑꢏꢮꢍꢐꢊꢙꢏꢊꢒꢔꢋꢈ ꢀꢄꢣꢮꢍꢐꢦꢋ ꢈ ꢊꢐꢈ ꢽꢉꢊꢘꢉꢈ ꢙꢉꢔꢈ ꢩꢏꢔꢣꢘꢍꢍꢏꢦꢊꢐꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ
ꢙꢉꢔꢈ ꢩꢖꢏꢊꢦꢖꢒꢈ ꢎꢐꢊꢙꢈ ꢩꢏꢔꢘꢔꢦꢔꢦꢈ ꢙꢉꢔꢈ ꢦꢍꢎꢮꢒꢔꢈ ꢊꢐꢙꢏꢑꢛꢍꢒꢔꢘꢎꢒꢑꢏꢈ ꢐꢎꢘꢒꢔꢍꢩꢉꢊꢒꢊꢘꢈ
ꢑꢙꢙꢑꢘꢵꢈꢮꢖꢈꢙꢉꢔꢈꢙꢏꢑꢐꢋꢚꢔꢏꢈꢍꢚꢈꢙꢉꢔꢈꢑꢏꢖꢒꢈꢧꢏꢍꢎꢩꢋꢈꢚꢏꢍꢛꢈꢙꢉꢔꢈꢺꢏꢊꢧꢐꢑꢏꢦꢈꢏꢔꢑꢧꢔꢐꢙꢋꢈ
ꢙꢍꢈꢮꢍꢙꢉꢈꢙꢉꢔꢈꢘꢑꢏꢮꢍꢐꢈꢑꢐꢦꢈꢐꢊꢙꢏꢍꢧꢔꢐꢈꢑꢙꢍꢛꢈꢍꢚꢈꢙꢉꢔꢈꢀ≡ꢄꢈꢧꢏꢍꢎꢩꢈꢫꢗꢘꢉꢔꢛꢔꢈꢡꢠꢈ
ꢙꢍꢩꢬꢟꢈ Fꢍꢏꢈ ꢙꢉꢊꢋꢈ ꢙꢏꢑꢐꢋꢚꢍꢏꢛꢑꢙꢊꢍꢐꢈ ꢑꢐꢈ ꢑꢹꢑꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ
ꢁ
ꢀ
!ꢄꢅꢆꢇꢁꢄꢈꢉꢊꢋꢌ/ꢋꢃꢂꢈꢉꢊꢋꢃꢉ Lꢄꢉꢍꢈꢍꢎꢍꢏ Üꢄꢈꢐꢃꢆꢉꢈꢍꢑꢍ Iꢃꢈꢒꢃꢓꢔꢃꢆꢇꢏ Lꢂ bꢃꢎꢃꢄꢋꢃꢈꢂꢃꢆ Cꢃꢓꢒ
ꢕꢖꢗꢏ "#$ꢕꢗ Iꢃꢈꢒꢃꢓꢔꢃꢆꢇꢏ Dꢃꢆꢂꢁꢄ&ꢀ
L/Da ꢌ 9)ꢎꢈ*ꢃ /Çaa ꢊꢀꢊꢀ $,ꢗ$ tꢓꢁꢊꢃ 9ꢀ .ꢁꢍꢁꢈꢓꢓꢅꢄ ꢘ0ꢗ#, aꢅꢄꢍ*ꢃꢓꢓꢈꢃꢆ ꢊꢃꢒꢃ1 ,ꢀ
ꢔꢀ
29ꢌꢂꢁꢈꢓ3 ꢓꢎꢍ4ꢀꢇꢁꢒꢃ5ꢎꢄꢈꢌꢋꢃꢈꢒꢃꢓꢔꢃꢆꢇꢀ
ꢈFꢍꢍꢙꢐꢍꢙꢔꢋꢈꢏꢔꢒꢑꢨꢐꢧꢈꢙꢍꢈꢙꢉꢔꢈꢨꢙꢒꢔꢈꢑꢐꢦ/ꢍꢏꢈꢑꢎꢙꢉꢍꢏꢋꢈꢋꢉꢍꢎꢒꢦꢈꢑꢩꢩꢔꢑꢏꢈꢉꢔꢏꢔꢟꢈꢈ
†
ꢪꢒꢔꢘꢙꢏꢍꢐꢊꢘꢈ ꢗꢎꢩꢩꢒꢔꢛꢔꢐꢙꢑꢏꢖꢈ ꢅꢐꢚꢍꢏꢛꢑꢙꢊꢍꢐꢈ ꢫꢪꢗꢅꢬꢈ ꢑꢭꢑꢊꢒꢑꢮꢒꢔꢯꢈ ꢰꢦꢔꢙꢑꢊꢒꢋꢈ ꢍꢚꢈ ꢑꢐꢖꢈ
ꢋꢎꢩꢩꢒꢔꢛꢔꢐꢙꢑꢏꢖꢈ ꢊꢐꢚꢍꢏꢛꢑꢙꢊꢍꢐꢈ ꢑꢭꢑꢊꢒꢑꢮꢒꢔꢈ ꢋꢉꢍꢎꢒꢦꢈ ꢮꢔꢈ ꢊꢐꢘꢒꢎꢦꢔꢦꢈ ꢉꢔꢏꢔꢱꢟꢈ ꢗꢔꢔꢈ
ꢲꢁꢅꢯꢈꢡꢝꢟꢡꢝꢢꢳ/ꢞꢝꢞꢞꢝꢝꢝꢝꢝꢞꢈ
ꢇꢉꢊꢋꢈꢌꢍꢎꢏꢐꢑꢒꢈꢊꢋꢈꢓꢈꢇꢉꢔꢈꢕꢍꢖꢑꢒꢈꢗꢍꢘꢊꢔꢙꢖꢈꢍꢚꢈꢀꢉꢔꢛꢊꢋꢙꢏꢖꢈꢜꢝꢞꢞ
Wꢀ bꢁꢂꢃꢟꢠꢈꢜꢝꢡꢢꢠꢈꢈꢈꢠꢈꢡꢣꢢꢈꢤꢈꢉꢈꢈ
ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ

ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ
ChemComm
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DOI: 10.1039/C8CC00478A
/haaÜbL/!ÇLhbꢈ
Wꢀꢁꢂꢃꢄꢅ bꢄꢆꢇꢈ
H/D
Ar
ꢈ
ꢀꢍꢛꢩꢒꢔꢞꢈÇꢑ&ꢀꢕꢈꢽꢑꢋꢈꢊꢋꢍꢒꢑꢙꢔꢦꢈꢩꢏꢊꢍꢏꢈꢙꢍꢈꢙꢉꢔꢈꢉꢖꢦꢏꢍꢒꢖꢙꢊꢘꢈꢽꢍꢏꢵꢣꢎꢩꢈ
N
H/D
ꢍꢚꢈ ꢙꢉꢔꢈꢩꢏꢍꢦꢎꢘꢙꢈ ꢛꢊꢞꢙꢎꢏꢔꢈ ꢮꢖꢈꢋꢍꢒꢭꢔꢐꢙꢈꢏꢔꢛꢍꢭꢑꢒꢈ ꢑꢐꢦꢈ ꢔꢞꢙꢏꢑꢘꢙꢊꢍꢐꢈꢍꢚꢈ
ꢙꢉꢔꢈꢋꢍꢒꢊꢦꢈꢏꢔꢋꢊꢦꢎꢔꢈꢽꢊꢙꢉꢈꢙꢍꢒꢎꢔꢐꢔ/ꢩꢔꢐꢙꢑꢐꢔꢈꢡꢝꢯꢡꢈꢚꢍꢒꢒꢍꢽꢔꢦꢈꢮꢖꢈꢦꢊꢏꢔꢘꢙꢈ
Ar
N
N
N
+
+
ꢘꢏꢖꢋꢙꢑꢒꢒꢊꢹꢑꢙꢊꢍꢐꢈ ꢑꢙꢈ ꣉ꢿꢝ꣌ꢀꢟꢈ ꢅꢐꢈ ꢙꢉꢊꢋꢈ ꢽꢑꢖꢈ ꢋꢊꢐꢧꢒꢔꢈ ꢘꢏꢖꢋꢙꢑꢒꢋꢈ ꢍꢚꢈ Çꢑ&ꢀꢕ
ꢈ
1. Ti(OiPr)4
H /D
ꢋꢎꢊꢙꢑꢮꢒꢔꢈ ꢚꢍꢏꢈ ꣂꢣꢏꢑꢖꢈ ꢦꢊꢚꢚꢏꢑꢘꢙꢊꢍꢐꢈ ꢽꢔꢏꢔꢈ ꢍꢮꢙꢑꢊꢐꢔꢦꢈ ꢑꢐꢦꢈ ꢙꢉꢔꢈ
2
. ArMgBr
ꢡ
ꢋꢩꢔꢘꢙꢏꢍꢋꢘꢍꢩꢊꢘꢈ ꢘꢉꢑꢏꢑꢘꢙꢔꢏꢊꢹꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢘꢍꢛꢩꢒꢔꢞꢈ ꢮꢖꢈ ꢶꢠꢈ ꢀ꣏ ꢶ꣐ꢈ
ꢡꢢ
ꢡ
D/H
H
N
H
ꢡꢳ
ꢡ
Ph4F
Ph3F
p-Tol
ꢑꢐꢦꢈ F꣏ ꢶ꣐ꢈ ꢄꢂꢕꢈ ꢋꢩꢔꢘꢙꢏꢍꢋꢘꢍꢩꢖꢈ ꢽꢑꢋꢈ ꢑꢘꢉꢊꢔꢭꢔꢦꢟꢈ ꢶꢖꢦꢏꢍꢒꢖꢋꢊꢋꢈ
ꢎꢑꢐꢙꢊꢙꢑꢙꢊꢭꢔꢒꢖꢈꢧꢑꢭꢔꢈꢙꢉꢔꢈꢏꢔꢑꢘꢙꢊꢍꢐꢈꢩꢏꢍꢦꢎꢘꢙꢈꢉꢕ
H/D
H
Ph3F
H
p-Tol
ꣅ
ꢟꢈ
Ph4F
N
N
N
N
N
1a/1a-d 2
1b
1c
7
3 %
73 %
dr = 15:1
46 %
dr = 14:1
dr = 11:1
H
N
H
N
H
N
Ph
Th
Ph4F
H
Ph
H
Th
H
Ph4F
N
N
N
1d
1e
1f
4
1 %
52 %
dr = 5:1
83 %
dr = 7:1
dr > 20:1
{
ꢍꢓꢇꢆꢇ %ꢈ ꢈ ꢲꢊꢑꢋꢙꢔꢏꢔꢍꢋꢔꢒꢔꢘꢙꢊꢭꢔꢈ ꢇꢊꢫꢁꢈꢥꢏꢬ
ꢿ
ꢣꢛꢔꢦꢊꢑꢙꢔꢦꢈ ꢦꢍꢎꢮꢒꢔꢈ ꢑꢏꢖꢒꢈ ꢺꢏꢊꢧꢐꢑꢏꢦꢈ
ꢣꢠꢈꢥꢉꢢF
ꢯꢈꢡꢟꢝꢈꢔꣅꢎꢊꢭꢠꢈꢕꢇꢠꢈꣀꢈꢛꢊꢐꢟꢈꢆꢏꢂꢧ꣈ꢏꢯꢈꢢꢟꣀꢈꢔꣅꢎꢊꢭꢠꢈ
꣊꣋꣌ꢀꢈꢦꢎꢏꢊꢐꢧꢈꢙꢉꢔꢈꢑꢦꢦꢊꢙꢊꢍꢐꢈꢙꢉꢔꢐꢈꢿꢝ꣌ꢀꢠꢈꢜꢈꢦꢑꢖꢋꢟꢈꢥꢏꢍꢙꢍꢐꢍꢒꢖꢋꢊꢋꢈꢽꢊꢙꢉꢈꢶ ꢁꢈꢫꢉꢄ* ꢉꢕꢬꢠꢈ
ꢑꢦꢦꢊꢙꢊꢍꢐꢋꢈꢙꢍꢈꢡꢠꢜꢣꢦꢊꢫꢩꢖꢏꢊꢦꢊꢐꢣꢜꢣꢖꢒꢬꢔꢙꢉꢖꢐꢔꢈꢑꢐꢦꢈꢦꢔꢏꢊꢭꢑꢙꢊꢭꢔꢋꢟ ꢥꢉꢿFꢈ꣇ꢈꢿꢣFꢣꢀ
꣇
꣄
ꢶ
ꢿ
ꢈ
꣄ ꢿ ꢿ
ꢈꢢꢣFꢣꢀ ꢶ ꢣꢠꢈꢇꢉꢈ꣇ꢈꢜꢣꢙꢉꢊꢔꢐꢖꢒꢟꢈꢈꢇꢊꢫꢁꢈꢥꢏꢬ
꣉
ꢜ
ꢲ
ꢜ
ꢁꢈꢫꢉꢄ&ꢒ
% ꢢ
ꢬꢈꢍꢏꢈꢀF ꢀꢁꢁꢶꢈꢫꢉ"&ꢇꢬꢟ
ꢈ
ꢇꢉꢔꢈꢊꢐꢊꢙꢊꢑꢒꢈꢩꢏꢍꢍꢚꢈꢍꢚꢈꢘꢍꢐꢘꢔꢩꢙꢈꢽꢑꢋꢈꢩꢏꢍꢭꢊꢦꢔꢦꢈꢮꢖꢈꢙꢉꢔꢈꢋꢙꢏꢑꢊꢧꢉꢙꢚꢍꢏꢽꢑꢏꢦꢈ
ꢈ
ꢍꢓꢇꢆꢇ 4 ꢥꢏꢍꢩꢍꢋꢔꢦꢈꢏꢔꢑꢘꢙꢊꢍꢐꢈꢩꢑꢙꢉꢽꢑꢖꢈꢚꢍꢏꢈꢙꢉꢔꢈꢋꢖꢐꢙꢉꢔꢋꢊꢋꢈꢍꢚꢈꢦꢊꢑꢏꢖꢒꢑꢙꢔꢦꢈ
{
ꢡꢠꢜꢣꢦꢊꢫꢩꢖꢏꢊꢦꢊꢐꢣꢜꢣꢖꢒꢬꢔꢙꢉꢑꢐꢔꢋ/ꢔꢙꢉꢔꢐꢔꢋꢟꢈꢆꢏꢈ꣇ꢈꢿꢣFꢣꢀ ꢣꢟ
ꢍꢐꢔꢣꢩꢍꢙꢈ ꢦꢊꢑꢏꢖꢒꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢡꢠꢜꢣꢦꢊꢫꢩꢖꢏꢊꢦꢊꢐꢣꢜꢣꢖꢒꢬꢔꢙꢉꢖꢐꢔꢈ ꢮꢖꢈ ꢘꢍꢐꢋꢔꢘꢎꢙꢊꢭꢔꢈ
꣄ ꢿ
ꢶ ꢈ
ꢑꢦꢦꢊꢙꢊꢍꢐꢈꢍꢚꢈꢑꢈꢋꢙꢍꢊꢘꢉꢊꢍꢛꢔꢙꢏꢊꢘꢈꢑꢛꢍꢎꢐꢙꢈꢍꢚꢈꢇꢊꢫꢁꢈꢥꢏꢬ ꢈꢑꢐꢦꢈꢢꢟꣀꢈꢔꣅꢎꢊꢭꢑꢒꢔꢐꢙꢋꢈ
ꢿ
ꢍꢚꢈ ꢑꢐꢈ ꢑꢏꢖꢒꢛꢑꢧꢐꢔꢋꢊꢎꢛꢈ ꢮꢏꢍꢛꢊꢦꢔꢈ ꢏꢔꢑꢧꢔꢐꢙꢈ ꢫꢗꢘꢉꢔꢛꢔꢈ ꢜꢬꢟꢈ ꢇꢉꢔꢈ ꢏꢔꢑꢘꢙꢊꢍꢐꢈ
ꢘꢍꢐꢦꢊꢙꢊꢍꢐꢋꢈ ꢽꢔꢏꢔꢈ ꢍꢩꢙꢊꢛꢊꢹꢔꢦꢈ ꢚꢍꢏꢈ ꢙꢉꢔꢈ ꢑꢦꢦꢊꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢿꢣ
ꢚꢒꢎꢍꢏꢍꢩꢉꢔꢐꢖꢒꢛꢑꢧꢐꢔꢋꢊꢎꢛꢈ ꢮꢏꢍꢛꢊꢦꢔꢈ ꢽꢉꢊꢘꢉꢈ ꢧꢑꢭꢔꢈ ꢙꢉꢔꢈ ꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢊꢐꢧꢈ
ꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢒꢵꢑꢐꢔꢈ ꢉꢄꢈ ꢊꢐꢈ ꢧꢍꢍꢦꢈ ꢖꢊꢔꢒꢦꢈ ꢎꢩꢍꢐꢈ ꢑꣅꢎꢔꢍꢎꢋꢈ ꢽꢍꢏꢵꢣꢎꢩꢟꢈ ꢇꢉꢔꢈ
ꢏꢑꢘꢔꢛꢑꢙꢔꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢁꢄꢍꢈꢈ ꢦꢊꢑꢋꢙꢔꢏꢔꢍꢊꢋꢍꢛꢔꢏꢈ ꢽꢑꢋꢈ ꢍꢮꢙꢑꢊꢐꢔꢦꢈ ꢑꢋꢈ ꢙꢉꢔꢈ ꢛꢑꢊꢐꢈ
ꢩꢏꢍꢦꢎꢘꢙꢈꢊꢐꢈꢑꢈꢦꢊꢑꢋꢙꢔꢏꢔꢍꢛꢔꢏꢊꢘꢈꢏꢑꢙꢊꢍꢈꢫꢦꢏꢬꢈꢍꢚꢈꢡꢿꢈꢯꢈꢡꢈꢽꢊꢙꢉꢈꢏꢔꢋꢩꢔꢘꢙꢈꢙꢍꢈꢙꢉꢔꢈ
ꢑꢒꢙꢔꢏꢐꢑꢙꢊꢭꢔꢈꢂꢃꢉꢅꢈꢩꢏꢍꢦꢎꢘꢙꢈꢫꢗꢘꢉꢔꢛꢔꢈꢜꢬꢟꢈ
ꢈ
ꢗꢊꢛꢊꢒꢑꢏꢒꢖꢠꢈꢊꢐꢈꢑꢒꢒꢈꢍꢙꢉꢔꢏꢈꢘꢑꢋꢔꢋꢈꢫꢉ"&ꢕꢬꢈꢙꢉꢔꢈꢉꢍꢛꢍꢘꢉꢊꢏꢑꢒꢈꢦꢊꢑꢋꢙꢔꢏꢔꢍꢛꢔꢏꢈ
ꢽꢑꢋꢈꢚꢍꢎꢐꢦꢈꢙꢍꢈꢮꢔꢈꢙꢉꢔꢈꢛꢑꢊꢐꢈꢩꢏꢍꢦꢎꢘꢙꢈꢽꢊꢙꢉꢈꢦꢏꢈꢭꢑꢒꢎꢔꢋꢈꢏꢑꢐꢧꢊꢐꢧꢈꢮꢔꢙꢽꢔꢔꢐꢈ
꣍ꢜꢝꢯꢡꢈ ꢑꢐꢦꢈ ꣀꢯꢡꢈ ꢫꢗꢘꢉꢔꢛꢔꢈ ꢜꢬꢟꢈ ꢇꢉꢔꢈ ꢊꢦꢔꢐꢙꢊꢚꢊꢘꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢛꢑꢌꢍꢏꢈ
ꢦꢊꢑꢋꢙꢔꢏꢔꢍꢛꢔꢏꢈꢑꢐꢦꢈꢙꢉꢔꢈꢦꢔꢙꢔꢏꢛꢊꢐꢑꢙꢊꢍꢐꢈꢍꢚꢈꢙꢉꢔꢈꢦꢏꢈꢭꢑꢒꢎꢔꢋꢈꢽꢑꢋꢈꢑꢘꢉꢊꢔꢭꢔꢦꢈ
ꢮꢖꢈꢄꢂꢕꢈꢋꢩꢔꢘꢙꢏꢍꢋꢘꢍꢩꢖꢈꢎꢋꢊꢐꢧꢈꢪꢎꢫꢉꢚꢘꢬ ꢈꢑꢋꢈꢘꢉꢊꢏꢑꢒꢈꢋꢉꢊꢚꢙꢈꢏꢔꢑꢧꢔꢐꢙꢟꢈꢈ
ꢢ
ꢢ
ꢲꢔꢎꢙꢔꢏꢍꢒꢖꢙꢊꢘꢈꢽꢍꢏꢵꢣꢎꢩꢈꢒꢔꢑꢦꢈꢙꢍꢈꢚꢎꢒꢒꢈꢦꢔꢎꢙꢔꢏꢑꢙꢊꢍꢐꢈꢍꢚꢈꢙꢉꢔꢈꢙꢽꢍꢈꢋꢩ ꢈ
ꢈ
ꢘꢑꢏꢮꢍꢐꢈꢑꢙꢍꢛꢋꢈꢫꢉꢄ&ꢒ%ꢬꢟꢈFꢎꢏꢙꢉꢔꢏꢛꢍꢏꢔꢈꢙꢉꢔꢈꢑꢦꢦꢊꢙꢊꢍꢐꢈꢍꢚꢈꢑꢐꢈꢔꢞꢘꢔꢋꢋꢈ
ꢍꢚꢈ ꢔꢒꢔꢛꢔꢐꢙꢑꢒꢈ ꢊꢍꢦꢊꢐꢔꢈ ꢮꢔꢚꢍꢏꢔꢈ ꢙꢉꢔꢈ ꢉꢖꢦꢏꢍꢒꢖꢙꢊꢘꢈ ꢋꢙꢔꢩꢈ ꢧꢑꢭꢔꢈ ꢊꢈꢉꢣꢡꢠꢜꢣ
ꢦꢊꢑꢏꢖꢒꢣꢡꢠꢜꢣꢦꢊꢫꢩꢖꢏꢊꢦꢊꢐꢣꢜꢣꢖꢒꢬꢔꢙꢉꢔꢐꢔꢈ ꢫ%ꢬ ꢊꢐꢈ ꣄ꢝ꣎ꢈ ꢖꢊꢔꢒꢦꢟꢈ ꢺꢊꢭꢔꢐꢈ ꢙꢉꢔꢋꢔꢈ
ꢔꢞꢩꢔꢏꢊꢛꢔꢐꢙꢑꢒꢈ ꢏꢔꢋꢎꢒꢙꢋꢠꢈ ꢑꢋꢈ ꢽꢔꢒꢒꢈ ꢑꢋꢈ ꢙꢉꢔꢈ ꢏꢔꢋꢎꢒꢙꢋꢈ ꢍꢚꢈ ꢍꢎꢏꢈ ꢩꢏꢔꢭꢊꢍꢎꢋꢈ
ꢋꢙꢎꢦꢖꢈꢍꢐꢈꢙꢉꢔꢈꢦꢊꢑꢏꢖꢒꢑꢙꢊꢍꢐꢈꢍꢚꢈꢙꢉꢔꢈꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢊꢐꢧꢈꢜꢣꢘꢖꢑꢐꢍꢩꢖꢏꢊꢦꢊꢐꢔꢋꢈ
ꢫꢭꢊꢦꢔꢈ ꢋꢎꢩꢏꢑꢬꢠꢈ ꢑꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢣꢮꢑꢋꢔꢦꢈ ꢏꢔꢑꢘꢙꢊꢍꢐꢈ ꢩꢑꢙꢉꢽꢑꢖꢈ ꢊꢋꢈ
ꢩꢏꢍꢩꢍꢋꢔꢦꢠꢈ ꢙꢉꢔꢈ ꢵꢔꢖꢈ ꢔꢒꢔꢛꢔꢐꢙꢋꢈ ꢍꢚꢈ ꢽꢉꢊꢘꢉꢈ ꢑꢏꢔꢈ ꢏꢔꢩꢏꢔꢋꢔꢐꢙꢔꢦꢈ ꢊꢐꢈ
ꢈ
Cꢑꢎꢁꢂꢇ ꢉ ꢂꢍꢒꢔꢘꢎꢒꢑꢏꢈꢋꢙꢏꢎꢘꢙꢎꢏꢔꢈꢍꢚꢈꢘꢍꢛꢩꢒꢔꢞꢈÇꢑ&ꢀꢕ ꢊꢋꢍꢒꢑꢙꢔꢦꢈꢚꢏꢍꢛꢈꢙꢉꢔꢈꢩꢏꢍꢦꢎꢘꢙꢈ
ꢛꢊꢞꢙꢎꢏꢔꢟꢈꢇꢉꢔꢏꢛꢑꢒꢈꢔꢒꢒꢊꢩꢋꢍꢊꢦꢋꢈꢋꢔꢙꢈꢑꢙꢈꢙꢉꢔꢈꣀꢝ꣎ꢈꢩꢏꢍꢮꢑꢮꢊꢒꢊꢙꢖꢈꢒꢔꢭꢔꢒꢟꢈꢶꢣꢑꢙꢍꢛꢋꢈ
ꢉꢑꢭꢔꢈ ꢮꢔꢔꢐꢈ ꢍꢛꢊꢙꢙꢔꢦꢈ ꢚꢍꢏꢈ ꢘꢒꢑꢏꢊꢙꢖꢟꢈ ꢗꢔꢒꢔꢘꢙꢔꢦꢈ ꢮꢍꢐꢦꢈ ꢒꢔꢐꢧꢙꢉꢋꢈ ꢫꢰ꣑ꢱꢬꢈ ꢑꢐꢦꢈ
ꢑꢐꢧꢒꢔꢋꢈꢫꢰ꣌ꢱꢬꢯꢈ ꢇꢊꢣꢀꢫꢡꢝꢬꢈ ꢜꢟꢢꢳꢡꣀꢫꢡꢜꢬꢠꢈ ꢇꢊꢣꢀꢫꢡ꣊ꢬ ꢜꢟꢡ꣊ꣀ꣊ꢫꢡꢜꢬꢠꢈ ꢇꢊꢣꢀꢫꢡꢬꢈ
ꢗꢘꢉꢔꢛꢔꢈꢢꢟꢈꢆꢐꢈꢑꢒꢵꢖꢐꢔꢈꢑꢏꢖꢒꢑꢙꢊꢍꢐ/ꢘꢍꢍꢏꢦꢊꢐꢑꢙꢊꢍꢐꢈꢋꢙꢔꢩꢈꢫLꢬꢈꢧꢊꢭꢔꢋꢈꢏꢊꢋꢔꢈ
ꢜꢟꢿ꣄꣋ꣀꢫꢡꢜꢬꢠꢈꢇꢊꢣꢀꢫꢜꢿꢬꢈꢜꢟ꣄ꢿ꣊꣄ꢫꢡꢜꢬꢠꢈꢇꢊꢣꢄꢫꢡꢬꢈꢡꢟꢳꢳꣀꢡꢫꢡꢡꢬꢠꢈꢇꢊꢣꢄꢫꢜꢬꢈꢜꢟꢡ꣋ꢳꢿꢫꢡꢡꢬꢠꢈ
ꢙꢍꢈ ꢑꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢊꢘꢈ ꢊꢐꢙꢔꢏꢛꢔꢦꢊꢑꢙꢔꢈ ꢫÇꢑ&ꢀꢈꢬꢟꢈ ꢗꢎꢘꢉꢈ ꢑꢈ ꢛꢍꢐꢍꢑꢏꢖꢒꢑꢙꢔꢦꢈ ꢀꢫꢡꢬꢣꢀꢫꢡꢝꢬꢈꢡꢟꢿꢝ꣋ꢿꢫꢡ꣊ꢬꢠꢈꢀꢫꢡꢝꢬꢣꢀꢫꢡ꣊ꢬꢈꢡꢟꢿꢳ꣊ꢝꢫꢡ꣄ꢬꢠꢈꢀꢫꢡ꣊ꢬꢣꢀꢫꢜꢿꢬꢈꢡꢟꢿ꣊ꣀꢿꢫꢡ꣊ꢬꢠꢈ
ꢁ
ꢣꢇꢊꢣꢀꢫꢜꢳꢬꢈꢡꢝꢳꢟꢿ꣊ꢫꣀꢬꢠꢈꢇꢊꢣꢁꢣꢀꢫꢢꣀꢬꢈꢡ꣊ꢜꢟ꣋꣄ꢫꢡꢝꢬꢠꢈꢀꢫꢡ꣊ꢬꢣꢇꢊꢣꢀꢫꢡꢝꢬꢈꢢ꣊ꢟ꣋ꢳꢫꢿꢬꢟꢈ
ꢑꢦꢦꢎꢘꢙꢈꢊꢋꢈꢔꢞꢩꢔꢘꢙꢔꢦꢈꢙꢍꢈ ꢔꢞꢉꢊꢮꢊꢙꢈꢩꢏꢍꢐꢍꢎꢐꢘꢔꢦꢈꢩꢍꢒꢑꢏꢊꢹꢑꢙꢊꢍꢐꢈꢑꢙꢈ ꢙꢉꢔꢈ
꣇ꢀꢈꢮꢍꢐꢦꢈꢦꢎꢔꢈꢙꢍꢈꢙꢉꢔꢈꢍꢏꢙꢉꢍꢣꢮꢏꢑꢐꢘꢉꢔꢦꢈꢩꢖꢏꢊꢦꢊꢐꢣꢜꢣꢖꢒꢔꢐꢔꢈꢋꢖꢋꢙꢔꢛꢟꢈ
ꢈ
ꢀ
ꢈ
ꢇꢉꢔꢈꢵꢔꢖꢈꢚꢔꢑꢙꢎꢏꢔꢋꢈꢍꢚꢈꢙꢉꢔꢈꢛꢍꢒꢔꢘꢎꢒꢑꢏꢈꢋꢙꢏꢎꢘꢙꢎꢏꢔꢈꢍꢚꢈꢘꢍꢛꢩꢒꢔꢞꢈÇꢑ&ꢀꢕ
ꢇꢉꢊꢋꢈ ꢽꢍꢎꢒꢦꢈ ꢚꢑꢭꢍꢎꢏꢈ ꢔꢊꢙꢉꢔꢏꢈ ꢑꢈ ꢦꢊꢏꢔꢘꢙꢈ ꢍꢏꢈ ꢣꢈ ꢑꢋꢈ ꢊꢐꢈ ꢙꢉꢔꢈ ꢘꢑꢋꢔꢈ ꢍꢚꢈ ꢙꢉꢔꢈ
ꢐꢊꢙꢏꢊꢒꢔꢈꢑꢐꢑꢒꢍꢧꢎꢔꢠꢈꢛꢔꢙꢑꢒꢈꢛꢔꢦꢊꢑꢙꢔꢦꢈꢋꢔꢘꢍꢐꢦꢈꢑꢏꢖꢒꢈꢑꢦꢦꢊꢙꢊꢍꢐꢈꢫLLꢠꢈÇꢑ&ꢀꢬꢟꢈ
ꢲꢔꢎꢙꢔꢏꢍꢒꢖꢋꢊꢋꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ ꢘꢍꢛꢩꢒꢔꢞꢈ Çꢑ&ꢀꢠꢈ ꢚꢊꢐꢑꢒꢒꢖꢈ
ꢧꢊꢭꢔꢋꢈ ꢙꢉꢔꢈ ꢔꢞꢩꢔꢘꢙꢔꢦꢈ ꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢒꢵꢑꢐꢔꢈ ꢫLLLꢠꢈ ꢉꢄ&ꢒ%ꢬꢠꢈ ꢽꢉꢊꢒꢔꢈ ꢏꢔꢑꢘꢙꢊꢍꢐꢈ
ꢦꢔꢩꢊꢘꢙꢔꢦꢈꢊꢐꢈFꢊꢧꢎꢏꢔꢈꢡꢈꢑꢏꢔꢈꢙꢉꢔꢈꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈꢛꢍꢙꢊꢚꢈꢑꢋꢈꢽꢔꢒꢒꢈ
ꢑꢋꢈ ꢙꢉꢔꢈ ꢑꢦꢦꢊꢙꢊꢍꢐꢑꢒꢈ ꢿꢣꢚꢒꢎꢍꢏꢍꢩꢉꢔꢐꢖꢒꢈ ꢧꢏꢍꢎꢩꢈ ꢽꢉꢊꢘꢉꢈ ꢊꢋꢈ ꢦꢊꢏꢔꢘꢙꢒꢖꢈ
ꢘꢍꢍꢏꢦꢊꢐꢑꢙꢔꢦꢈꢙꢍꢈꢙꢉꢔꢈꢛꢔꢙꢑꢒꢟꢈꢄꢍꢙꢑꢮꢒꢖꢠꢈꢙꢉꢔꢈꢙꢽꢍꢈꢉꢔꢙꢔꢏꢍꢑꢏꢖꢒꢈꢧꢏꢍꢎꢩꢋꢈ
ꢘꢍꢍꢏꢦꢊꢐꢑꢙꢔꢈꢙꢍꢈꢙꢉꢔꢈꢛꢔꢙꢑꢒꢈꢘꢔꢐꢙꢔꢏꢈꢽꢊꢙꢉꢈꢭꢔꢏꢖꢈꢦꢊꢚꢚꢔꢏꢔꢐꢙꢈꢇꢊꢣꢄꢈꢮꢍꢐꢦꢈ
ꢒꢔꢐꢧꢙꢉꢋꢈꢰꢇꢊꢣꢄꢫꢡꢬꢈꢡꢟꢳꢳꣀꢡꢫꢡꢡꢬꢠꢈꢇꢊꢣꢄꢫꢜꢬ ꢜꢟꢡ꣋ꢳꢿꢫꢡꢡꢬꢱꢟꢈꢇꢉꢊꢋꢈꢮꢏꢔꢑꢘꢉꢈꢍꢚꢈ
ꢽꢊꢙꢉꢈꢊꢍꢦꢊꢐꢔꢈꢽꢍꢎꢒꢦꢈꢍꢞꢊꢦꢑꢙꢊꢭꢔꢒꢖꢈꢏꢔꢒꢔꢑꢋꢔꢈꢑꢈꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢒꢵꢔꢐꢔꢈꢫLëꢠꢈ%ꢬꢟꢈ
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ꢈꢤꢈWꢀ bꢁꢂꢃꢟꢠꢈꢜꢝꢡꢜꢠꢈꢈꢈꢠꢈꢡꢣꢢꢈ
ꢇꢉꢊꢋꢈꢌꢍꢎꢏꢐꢑꢒꢈꢊꢋꢈꢓꢈꢇꢉꢔꢈꢕꢍꢖꢑꢒꢈꢗꢍꢘꢊꢔꢙꢖꢈꢍꢚꢈꢀꢉꢔꢛꢊꢋꢙꢏꢖꢈꢜꢝꢞꢞꢈ
ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ

ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ
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DOI: 10.1039/C8CC00478A
Wꢀꢁꢂꢃꢄꢅ bꢄꢆꢇ
ꢋꢖꢛꢛꢔꢙꢏꢖꢈ ꢑꢒꢋꢍꢈ ꢙꢏꢑꢐꢋꢒꢑꢙꢔꢋꢈ ꢙꢍꢈ ꢙꢉꢔꢈ ꢙꢽꢍꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ
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ꢆꢋꢈ ꢑꢈ ꢏꢔꢋꢎꢒꢙꢠꢈ ꢙꢉꢔꢈ ꢄꢸꢂꢁꢈ ꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢊꢐꢧꢈ ꢙꢍꢈ ꢙꢉꢔꢈ ꢇꢊꢣꢀꢫꢡꢝꢬꢈ σꢣ
ꢘꢑꢏꢮꢍꢐꢈꢑꢙꢍꢛꢋꢈꢽꢊꢙꢉꢈꢮꢍꢐꢦꢈꢒꢔꢐꢧꢙꢉꢋꢈꢍꢚꢈꢜꢟꢢꢳꢡꣀꢫꢡꢜꢬꢈꢑꢐꢦꢈꢜꢟꢡ꣊ꣀ꣊ꢫꢡꢜꢬꢈ ꢮꢍꢐꢦꢈ ꢍꢐꢒꢖꢈ ꢘꢍꢐꢙꢑꢊꢐꢋꢈ ꣄ꢿ꣎ꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢩꢑꢏꢔꢐꢙꢈ ꢄ꣈ꢁꢈ ꢘꢉꢑꢏꢑꢘꢙꢔꢏꢟꢈ ꢇꢉꢔꢈ
ꢚꢍꢏꢈꢇꢊꢣꢀꢫꢡꢝꢬꢈꢑꢐꢦꢈꢇꢊꢣꢀꢫꢡ꣊ꢬꢠꢈꢏꢔꢋꢩꢔꢘꢙꢊꢭꢔꢒꢖꢟꢈꢇꢉꢔꢋꢔꢈꢍꢮꢋꢔꢏꢭꢔꢦꢈꢭꢑꢒꢎꢔꢋꢈ ꢏꢔꢛꢑꢊꢐꢊꢐꢧꢈ ꢔꢒꢔꢘꢙꢏꢍꢐꢈ ꢦꢔꢐꢋꢊꢙꢖꢈ ꢽꢊꢙꢉꢊꢐꢈ ꢙꢉꢊꢋꢈ ꢄꢸꢂꢁꢈ ꢊꢋꢈ ꢋꢩꢏꢔꢑꢦꢈ ꢍꢭꢔꢏꢈ
ꢒꢊꢔꢈ ꢽꢊꢙꢉꢊꢐꢈ ꢙꢉꢔꢈ ꢔꢞꢩꢔꢘꢙꢔꢦꢈ ꢒꢔꢐꢧꢙꢉꢈ ꢏꢑꢐꢧꢔꢈ ꢚꢍꢏꢈ ꢚꢎꢐꢘꢙꢊꢍꢐꢑꢒꢊꢹꢔꢦꢈ ꢙꢉꢔꢈ πꢣꢋꢖꢋꢙꢔꢛꢈ ꢑꢐꢦꢈ ꢦꢔꢒꢍꢘꢑꢒꢊꢹꢔꢦꢈ ꢍꢐꢙꢍꢈ ꢇꢊꢠꢈ ꢄꢫꢡꢬꢠꢈ ꢀꢫꢡꢬꢠꢈ ꢑꢐꢦꢈ ꢀꢫꢡꢝꢬꢈ
ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢋꢟ ꢈ ꢇꢉꢔꢈ ꢀꢫꢡꢬꢣꢀꢫꢡꢝꢬꢈ ꢮꢍꢐꢦꢈ ꢊꢋꢈ ꢘꢍꢐꢋꢊꢦꢔꢏꢑꢮꢒꢖꢈ ꢫFꢊꢧꢎꢏꢔꢈ ꢜꢬꢟꢈ ꢅꢐꢈ ꢙꢉꢔꢈ ꢄ꣈ꢁꢈ ꢑꢐꢑꢒꢖꢋꢊꢋꢈ ꢍꢚꢈ {ꢐꢂ%ꢠꢈ ꢙꢉꢔꢈ ꢇꢊꢣꢄꢫꢡꢬꢈ ꢄ꣈ꢁꢈ
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ꢋꢉꢍꢏꢙꢔꢏꢈꢙꢉꢑꢐꢈꢙꢉꢔꢈꢀꢫꢡ꣊ꢬꢣꢀꢫꢜꢿꢬꢈꢮꢍꢐꢦꢈꢰꢡꢟꢿꢝ꣋ꢿꢫꢡ꣊ꢬꢈꢭꢋꢟꢈꢡꢟꢿ꣊ꣀꢿꢫꢡ꣊ꢬꢈ ꢔꢋꢋꢔꢐꢙꢊꢑꢒꢒꢖꢈ ꢊꢐꢭꢍꢒꢭꢔꢋꢈ ꢑꢈ ꢩꢈ ꢑꢙꢍꢛꢊꢘꢈ ꢍꢏꢮꢊꢙꢑꢒꢈ ꢫꢆꢁꢬꢈ ꢍꢐꢈ ꢄꢫꢡꢬꢈ ꢽꢊꢙꢉꢈ ꢑꢈ
꣑
ꢠꢈ ꢏꢔꢋꢩꢔꢘꢙꢊꢭꢔꢒꢖꢱꢠꢈ ꢽꢉꢊꢘꢉꢈ ꢊꢋꢈ ꢘꢍꢐꢋꢊꢋꢙꢔꢐꢙꢈ ꢽꢊꢙꢉꢈ ꢋꢍꢛꢔꢈ ꢦꢍꢎꢮꢒꢔꢈ ꢮꢍꢐꢦꢈ ꢩꢍꢩꢎꢒꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢡꢟ꣄ꢜꣀꢈ ꢔꢈ ꢫFꢊꢧꢎꢏꢔꢈ ꢢꢬꢟꢈ ꢇꢉꢔꢈ ꢛꢑꢊꢐꢈ ꢦꢔꢒꢍꢘꢑꢒꢊꢹꢑꢙꢊꢍꢐꢈ
ꢘꢉꢑꢏꢑꢘꢙꢔꢏꢈꢍꢚꢈꢙꢉꢔꢈꢚꢍꢏꢛꢔꢏꢟꢈꢈ ꢩꢑꢙꢙꢔꢏꢐꢈ ꢊꢐꢭꢍꢒꢭꢔꢋꢈ ꢙꢉꢔꢈ ꢇꢊꢣꢄꢫꢡꢬꢈ ꢣꢮꢍꢐꢦꢈ ꢙꢉꢑꢙꢈ ꢊꢐꢙꢔꢏꢑꢘꢙꢋꢈ ꢽꢊꢙꢉꢈ ꢙꢉꢔꢈ
ꢇꢉꢏꢔꢔꢈ ꢋꢊꢐꢧꢒꢔꢙꢋꢈ ꢍꢚꢈ ꢋꢑꢛꢔꢈ ꢊꢐꢙꢔꢐꢋꢊꢙꢖꢈ ꢊꢐꢈ ꢙꢉꢔꢈ F꣏ ꢶ꣐ꢈ ꢄꢂꢕꢈ ꢭꢊꢘꢊꢐꢑꢒꢈ ꢈꢘꢍꢛꢩꢍꢐꢔꢐꢙꢈꢮꢔꢙꢽꢔꢔꢐꢈꢀꢫꢡꢬꢈꢑꢐꢦꢈꢀꢫꢡꢝꢬꢈꢫ ꢈ꣇ꢈꣀꢝꢟ꣋ꢈꢵꢘꢑꢒꢈ
ꢋꢩꢔꢘꢙꢏꢎꢛꢈꢍꢚꢈÇꢑ&ꢀꢕꢈꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢈꢙꢍꢈꢙꢉꢔꢈꢙꢉꢏꢔꢔꢈꢘꢉꢔꢛꢊꢘꢑꢒꢒꢖꢈꢦꢊꢋꢙꢊꢐꢘꢙꢈꢿꢣ ꢛꢍꢒ ꢬꢟꢈ ꢇꢉꢔꢈ ꢏꢔꢋꢎꢒꢙꢊꢐꢧꢈ ꢄꢸꢂꢁꢈ ꢚꢍꢏꢈ ꢇꢊꢣꢄꢫꢡꢬꢈ ꢏꢔꢙꢑꢊꢐꢋꢈ ꣋ꢝ꣎ꢈ ꢍꢚꢈ ꢙꢉꢔꢈ
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ꢙꢉꢔꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ ꢘꢑꢏꢮꢍꢐꢈ ꢑꢙꢍꢛꢋꢈ ꢏꢔꢋꢍꢐꢑꢙꢔꢈ ꢑꢙꢈ ꣋ꢳꢟꢡꢈ ꢑꢐꢦꢈ ꢦꢔꢐꢋꢊꢙꢖꢈꢮꢔꢊꢐꢧꢈꢒꢍꢘꢑꢙꢔꢦꢈꢊꢐꢈꢙꢉꢔꢈ
ꢡꢡꢝꢟꢢꢈ ꢩꢩꢛꢠꢈ ꢙꢉꢎꢋꢈ ꢘꢍꢐꢚꢊꢏꢛꢊꢐꢧꢈ ꢑꢈ ꢩꢏꢍꢐꢍꢎꢐꢘꢔꢦꢈ ꢑꢋꢖꢛꢛꢔꢙꢏꢖꢈ ꢊꢐꢈ ꢙꢉꢔꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢀꢫꢡꢬꢣꢀꢫꢡꢝꢬꢈ ꢣꢮꢍꢐꢦꢈ ꢑꢋꢈ ꢊꢒꢒꢎꢋꢙꢏꢑꢙꢔꢦꢈ ꢊꢐꢈ Fꢊꢧꢎꢏꢔꢈ ꢢꢟꢈ ꢇꢉꢔꢈ ꢄ꣈ꢁꢈ
ꢈ
ꢅꢐꢈꢙꢉꢔꢈ ꢀꢈꢄꢂꢕꢈꢋꢩꢔꢘꢙꢏꢎꢛꢈ ꢩꢑꢏꢔꢐꢙꢈ ꢄ꣈ꢁꢈ ꢘꢉꢑꢏꢑꢘꢙꢔꢏꢠꢈ ꢙꢉꢔꢈ ꢏꢔꢛꢑꢊꢐꢊꢐꢧꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢜꢔꢈ ꢔꢒꢔꢘꢙꢏꢍꢐꢈ
π
ꢣꢋꢖꢋꢙꢔꢛꢈꢍꢚꢈꢙꢉꢔꢈꣅꢎꢊꢐꢍꢒꢊꢐꢔꢈꢏꢊꢐꢧꢈꢑꢐꢦꢈ
π
ꢋꢖꢋꢙꢔꢛꢟꢈꢀꢍꢛꢩꢒꢔꢞꢈ Çꢑ&ꢀꢄꢠ ꢍꢮꢙꢑꢊꢐꢔꢦꢈꢑꢋꢈꢦꢔꢋꢘꢏꢊꢮꢔꢦꢈ ꢚꢍꢏꢈ Çꢑ&ꢀꢕꢈꢔꢞꢘꢔꢩꢙꢈ ꢑꢐꢑꢒꢖꢋꢊꢋꢈꢍꢚꢈ{ꢐꢂꢉꢈꢑꢐꢦꢈ{ꢐꢂ%ꢈꢩꢍꢊꢐꢙꢋꢈꢘꢒꢔꢑꢏꢒꢖꢈꢙꢍꢈꢑꢈꢦꢔꢋꢘꢏꢊꢩꢙꢊꢍꢐꢈꢍꢚꢈꢙꢉꢔꢈ
ꢚꢍꢏꢈꢋꢙꢑꢏꢙꢊꢐꢧꢈꢚꢏꢍꢛꢈꢙꢉꢔꢈꢘꢍꢎꢩꢒꢊꢐꢧꢈꢩꢏꢍꢙꢍꢘꢍꢒꢈꢦꢔꢋꢘꢏꢊꢮꢔꢦꢈꢚꢍꢏꢈꢉꢄꢈ ꢫꢋꢔꢔꢈ ꢔꢒꢔꢘꢙꢏꢍꢐꢊꢘꢈꢋꢙꢏꢎꢘꢙꢎꢏꢔꢈꢍꢚꢈÇꢑ&ꢀꢕꢈꢑꢋꢈꢑꢐꢈꢔꢐꢔꢣꢑꢛꢊꢦꢍꢈꢽꢊꢙꢉꢈꢑꢈꢋꢊꢧꢐꢊꢚꢊꢘꢑꢐꢙꢈ
ꢗꢅꢬꢠꢈ ꢋꢉꢍꢽꢔꢦꢈ ꢚꢎꢒꢒꢖꢈ ꢘꢍꢐꢧꢏꢎꢔꢐꢙꢈ ꢋꢩꢔꢘꢙꢏꢍꢋꢘꢍꢩꢊꢘꢈ ꢚꢔꢑꢙꢎꢏꢔꢋꢠꢈ ꢉꢔꢐꢘꢔꢈ ꢏꢔꢋꢍꢐꢑꢐꢘꢔꢈꢮꢔꢙꢽꢔꢔꢐꢈꢙꢉꢔꢈꢐꢊꢙꢏꢍꢧꢔꢐꢣꢘꢔꢐꢙꢔꢏꢔꢦꢈꢩꢈꢆꢁꢈꢑꢐꢦꢈꢙꢉꢔꢈꢀꢫꢡꢬꢣ
ꢔꢞꢘꢒꢎꢦꢊꢐꢧꢈ ꢑꢐꢖꢈ ꢏꢍꢒꢔꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꣅꢎꢊꢐꢍꢒꢖꢒꢈ ꢧꢏꢍꢎꢩꢈ ꢊꢐꢈ ꢙꢉꢔꢈ ꢍꢮꢋꢔꢏꢭꢔꢦꢈ ꢀꢫꢡꢝꢬꢈπꢣꢮꢍꢐꢦꢟꢈꢈ
ꢑꢋꢖꢛꢛꢔꢙꢏꢖꢈꢍꢚꢈꢙꢉꢔꢈꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈꢎꢐꢊꢙꢟ
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Cꢑꢎꢁꢂꢇ 4ꢈꢀꢍꢛꢩꢑꢏꢊꢋꢍꢐꢈꢮꢔꢙꢽꢔꢔꢐꢈꢙꢉꢔꢈꢋꢙꢏꢊꢘꢙꢒꢖꢈꢒꢍꢘꢑꢒꢊꢹꢔꢦꢈꢄ꣈ꢁꢈꢑꢋꢋꢍꢘꢊꢑꢙꢔꢦꢈꢙꢍꢈꢙꢉꢔꢈꢇꢊꢣ
ꢈ
ꢍꢓꢇꢆꢇ . ꢇꢉꢔꢈ ꢵꢔꢖꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ ꢫ{ꢐꢂꢉꢬꢈ ꢑꢐꢦꢈ ꢔꢐꢔꢑꢛꢊꢦꢍꢙꢊꢙꢑꢐꢊꢎꢛꢈ
ꢄꢫꢡꢬꢈꢮꢍꢐꢦꢈꢑꢐꢦꢈꢙꢉꢔꢈꢦꢔꢒꢍꢘꢑꢒꢊꢹꢔꢦꢈꢋꢊꢙꢎꢑꢙꢊꢍꢐꢈꢊꢐꢈꢙꢉꢔꢈꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢊꢐꢧꢈꢄꢸꢂꢁꢈꢚꢍꢏꢈꢙꢉꢔꢈ
{
ꢸ
ꢔꢽꢊꢋꢈꢋꢙꢏꢎꢘꢙꢎꢏꢔꢈ{ꢐꢂ%ꢟꢈ
ꢫ
ꢈ
ꢈ
{ꢐꢂ%ꢬꢈꢏꢔꢋꢍꢐꢑꢐꢘꢔꢈꢋꢙꢏꢎꢘꢙꢎꢏꢔꢋꢈꢍꢚꢈÇꢑ&ꢀꢕ
ꢟ
ꢇꢉꢔꢈ ꢮꢍꢐꢦꢊꢐꢧꢈ ꢋꢊꢙꢎꢑꢙꢊꢍꢐꢈ ꢊꢐꢈ Çꢑ&ꢀꢕ ꢛꢑꢖꢈ ꢮꢔꢈ ꢦꢔꢋꢘꢏꢊꢮꢔꢦꢈ ꢽꢊꢙꢉꢈ
ꢏꢔꢚꢔꢏꢔꢐꢘꢔꢈ ꢙꢍꢈ ꢙꢽꢍꢈ ꢒꢊꢛꢊꢙꢊꢐꢧꢈ ꢋꢙꢏꢎꢘꢙꢎꢏꢔꢋꢯꢈ ꢑꢈ ꢘꢒꢑꢋꢋꢊꢘꢑꢒꢈ
ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ ꢽꢊꢙꢉꢈ ꢑꢈ ꢘꢍꢍꢏꢦꢊꢐꢑꢙꢔꢦꢈ ꣅꢎꢊꢐꢍꢒꢊꢐꢔꢈ ꢫ{ꢐꢂꢉꢠꢈ
ꢗꢘꢉꢔꢛꢔꢈ ꢿꢠꢈ ꢒꢔꢚꢙꢬꢠꢈ ꢍꢏꢈ ꢑꢐꢈ ꢔꢐꢔꢣꢑꢛꢊꢦꢍꢈ ꢙꢖꢩꢔꢈ ꢦꢔꢋꢘꢏꢊꢩꢙꢊꢍꢐꢈ ꢫ{ꢐꢂ%ꢠꢈ
ꢗꢘꢉꢔꢛꢔꢈꢿꢠꢈꢏꢊꢧꢉꢙꢬꢟꢈ꣈ꢢꢸ꣒ꢥ/꣄ꢣꢢꢡꢡꢺꢈꢧꢔꢍꢛꢔꢙꢏꢖꢈꢍꢩꢙꢊꢛꢊꢹꢑꢙꢊꢍꢐꢈꢍꢚꢈÇꢑ&ꢀꢕ
ꢑꢋꢈꢘꢑꢏꢏꢊꢔꢦꢈꢍꢎꢙꢈꢑꢐꢦꢈꢙꢉꢔꢈꢘꢑꢒꢘꢎꢒꢑꢙꢔꢦꢈꢧꢔꢍꢛꢔꢙꢏꢖꢈꢽꢑꢋꢈꢚꢍꢎꢐꢦꢈꢙꢍꢈꢮꢔꢈ
ꢊꢐꢈ ꢧꢍꢍꢦꢈ ꢑꢧꢏꢔꢔꢛꢔꢐꢙꢈ ꢽꢊꢙꢉꢈ ꢙꢉꢔꢈ ꢔꢞꢩꢔꢏꢊꢛꢔꢐꢙꢑꢒꢈ ꢦꢑꢙꢑꢟꢈ ꢆꢈ ꢄꢑꢙꢎꢏꢑꢒꢈ
ꢍꢐꢦꢊꢐꢧꢈ ꢁꢏꢮꢊꢙꢑꢒꢈ ꢫꢄ꣈ꢁꢬꢈ ꢑꢐꢑꢒꢖꢋꢊꢋꢈ ꢋꢩꢔꢘꢊꢚꢊꢘꢑꢒꢒꢖꢈ ꢚꢍꢏꢈ ꢙꢉꢔꢈ ꢏꢔꢋꢍꢐꢑꢐꢘꢔꢈ
ꢐꢂꢉꢈꢊꢐꢦꢊꢘꢑꢙꢔꢋꢈꢙꢉꢑꢙꢈꢙꢉꢔꢈꢇꢊꢣꢀꢫꢡꢝꢬꢈꢄ꣈ꢁꢈꢊꢋꢈꢏꢑꢙꢉꢔꢏꢈꢽꢔꢑꢵꢒꢖꢈꢩꢍꢩꢎꢒꢑꢙꢔꢦꢈ
ꢚꢍꢏꢈ ꢑꢈ ꢣꢮꢍꢐꢦꢈ ꢫꢡꢟꢢꢿ꣋ꢈ ꢔꢬꢠꢈ ꢽꢉꢔꢐꢈ ꢘꢍꢛꢩꢑꢏꢔꢦꢈ ꢙꢍꢈ ꢙꢉꢔꢈꢇꢊꢣꢀꢫꢡ꣊ꢬꢈꢄ꣈ꢁꢈ
ꢈ
ꢽ
꣈
{
σ
ꢫꢡꢟ꣄꣋ꢳꢈ ꢔꢬꢟꢈ ꢂꢍꢏꢔꢍꢭꢔꢏꢠꢈ ꢙꢉꢔꢈ ꢋꢔꢘꢍꢐꢦꢣꢍꢏꢦꢔꢏꢈ ꢩꢔꢏꢙꢎꢏꢮꢑꢙꢊꢍꢐꢈ ꢔꢐꢔꢏꢧꢖꢈ Cꢑꢎꢁꢂꢇ . ꢈ꣈ꢍꢐꢦꢈꢫꢧꢏꢔꢔꢐꢬꢈꢑꢐꢦꢈꢏꢊꢐꢧꢈꢫꢏꢔꢦꢬꢈꢘꢏꢊꢙꢊꢘꢑꢒꢈꢩꢍꢊꢐꢙꢋꢈꢏꢔꢋꢎꢒꢙꢊꢐꢧꢈꢚꢏꢍꢛꢈꢑꢐꢈꢆꢅꢂꢈ
ꢑꢐꢑꢒꢖꢋꢊꢋꢈꢍꢚꢈꢙꢉꢔꢈꢔꢒꢔꢘꢙꢏꢍꢐꢊꢘꢈꢋꢙꢏꢎꢘꢙꢎꢏꢔꢈꢍꢚꢈÇꢑ&ꢀꢕꢟꢈ
ꢑꢐꢑꢒꢖꢋꢊꢋꢈ ꢋꢉꢍꢽꢔꢦꢈ ꢑꢈ ꢋꢙꢏꢍꢐꢧꢈ ꢦꢔꢒꢍꢘꢑꢒꢊꢹꢑꢙꢊꢍꢐꢈ ꢘꢍꢛꢩꢍꢐꢔꢐꢙꢈ ꢍꢚꢈ ꢙꢉꢔꢈ
ꢻ
ꢔꢒꢔꢘꢙꢏꢍꢐꢈ ꢦꢔꢐꢋꢊꢙꢖꢈ ꢍꢚꢈ
ꢣꢡ
σ
ꢘꢑꢒꢈꢛꢍꢒ ꢬꢈꢫFꢊꢧꢎꢏꢔꢈꢜꢬꢟꢈꢈ
ꢰꢇꢊꢣꢀꢫꢡꢝꢬꢱꢈ ꢊꢐꢙꢍꢈ
π
ꢰꢄꢫꢡꢬꢣꢀꢫꢡꢬꢱꢈ ꢫ
∆
ꢪ
ꢜ
ꢈ ꣇ꢈ ꢡ꣊ꢡꢈ
ꢇꢉꢔꢈꢆꢅꢂꢈꢑꢐꢑꢒꢖꢋꢊꢋꢈꢍꢚꢈꢙꢉꢔꢈꢔꢒꢔꢘꢙꢏꢍꢐꢈꢦꢔꢐꢋꢊꢙꢖꢈꢍꢚꢈÇꢑ&ꢀꢕꢈꢘꢍꢐꢚꢊꢏꢛꢋꢈꢙꢉꢔꢈꢄ꣈ꢁꢈ
ꢑꢐꢑꢒꢖꢋꢊꢋꢈꢫFꢊꢧꢎꢏꢔꢈꢿꢬꢟꢈꢇꢉꢔꢏꢔꢈꢊꢋꢈꢐꢍꢈꢮꢍꢐꢦꢈꢘꢏꢊꢙꢊꢘꢑꢒꢈꢩꢍꢊꢐꢙꢈꢫ꣈ꢀꢥꢬꢈꢮꢔꢙꢽꢔꢔꢐꢈꢇꢊꢈ
ꢑꢐꢦꢈꢀꢫꢡꢝꢬꢠꢈꢽꢉꢔꢏꢔꢑꢋꢈꢙꢉꢔꢏꢔꢈꢊꢋꢈꢍꢐꢔꢈꢮꢔꢙꢽꢔꢔꢐꢈꢇꢊꢈꢑꢐꢦꢈꢀꢫꢡ꣊ꢬꢟꢈꢅꢐꢈꢑꢦꢦꢊꢙꢊꢍꢐꢠꢈ
ꢙꢉꢔꢈꢭꢑꢒꢎꢔꢋꢈꢍꢚꢈꢙꢉꢔꢈꢔꢒꢒꢊꢩꢙꢊꢘꢊꢙꢖꢈεꢈꢑꢙꢈꢭꢑꢏꢊꢍꢎꢋꢈ꣈ꢀꢥꢋꢈꢑꢏꢔꢈꢊꢐꢈꢑꢧꢏꢔꢔꢛꢔꢐꢙꢈꢽꢊꢙꢉꢈ
ꢙꢉꢔꢈꢦꢔꢋꢘꢏꢊꢩꢙꢊꢍꢐꢈꢍꢚꢈꢇꢊꢣꢈꢚꢈꢑꢋꢈꢑꢐꢈꢔꢐꢔꢣꢑꢛꢊꢦꢍꢈꢘꢍꢛꢩꢒꢔꢞꢟꢈFꢍꢏꢈꢙꢉꢔꢈꢙꢽꢍꢈ꣈ꢀꢥꢋꢈ
ꢮꢔꢙꢽꢔꢔꢐꢈ ꢇꢊꢈ ꢑꢐꢦꢈ ꢄꢠꢈ ꢙꢉꢑꢙꢈ ꢑꢋꢋꢍꢘꢊꢑꢙꢔꢦꢈ ꢽꢊꢙꢉꢈ ꢇꢊꢣꢄꢫꢡꢬꢈ ꢉꢑꢋꢈ εꢈ ꣇ꢈ ꢝꢟꢡꢿꢜꢠꢈ
ꢵ
ꢽ
ꢉꢔꢏꢔꢑꢋꢈꢙꢉꢑꢙꢈꢚꢍꢏꢈꢇꢊꢣꢄꢫꢜꢬꢈꢉꢑꢋꢈεꢈ꣇ꢈꢝꢟꢝꢜꢜꢟ ꢇꢉꢊꢋꢈꢘꢒꢔꢑꢏꢒꢖꢈꢊꢐꢦꢊꢘꢑꢙꢔꢋꢈꢛꢍꢏꢔꢈ
ꢦꢔꢭꢔꢒꢍꢩꢔꢦꢈπꢣꢘꢉꢑꢏꢑꢘꢙꢔꢏꢈꢚꢍꢏꢈꢙꢉꢔꢈꢮꢍꢐꢦꢈꢮꢔꢙꢽꢔꢔꢐꢈꢇꢊꢈꢑꢐꢦꢈꢄꢫꢡꢬꢈꢽꢉꢊꢒꢔꢈꢙꢉꢔꢈ
ꢭꢑꢒꢎꢔꢋꢈ ꢍꢚꢈ εꢈ ꢚꢍꢏꢈ ꢙꢉꢔꢈ ꢄꢫꢡꢬꢣꢀꢫꢡꢬꢠꢈ ꢀꢫꢡꢬꢣꢀꢫꢡꢝꢬꢈ ꢑꢐꢦꢈ ꢀꢫꢡꢝꢬꢣꢀꢫꢡ꣊ꢬꢈ ꢫꢝꢟꢝꣀꢜꢠꢈ
ꢝꢟꢜꢜꢿꢈꢑꢐꢦꢈꢝꢟꢡꢜꢜꢠꢈꢏꢔꢋꢩꢔꢘꢙꢊꢭꢔꢒꢖꢬ ꢑꢒꢋꢍꢈꢏꢔꢚꢒꢔꢘꢙꢈꢑꢈꢋꢙꢏꢍꢐꢧꢔꢏꢈπꢣꢘꢍꢛꢩꢍꢐꢔꢐꢙꢈ
ꢚꢍꢏꢈꢙꢉꢔꢈꢀꢫꢡꢬꢣꢀꢫꢡꢝꢬꢈꢮꢍꢐꢦꢈꢑꢐꢦꢈꢑꢈꢋꢊꢧꢐꢊꢚꢊꢘꢑꢐꢙꢈσꢣꢘꢉꢑꢏꢑꢘꢙꢔꢏꢈꢚꢍꢏꢈꢙꢉꢔꢈꢄꢫꢡꢬꢣ
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ꢈ
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Çꢑ&/'ꢉꢈ( b[ah
Cꢑꢎꢁꢂꢇ %ꢈꢀꢍꢛꢩꢑꢏꢊꢋꢍꢐꢈꢮꢔꢙꢽꢔꢔꢐꢈꢙꢉꢔꢈꢋꢙꢏꢊꢘꢙꢒꢖꢈꢒꢍꢘꢑꢒꢊꢹꢔꢦꢈꢄ꣈ꢁꢈꢑꢋꢋꢍꢘꢊꢑꢙꢔꢦꢈꢙꢍꢈꢙꢉꢔꢈꢇꢊꢣ
ꢫꢡꢝꢬꢈꢮꢍꢐꢦꢈꢑꢐꢦꢈꢙꢉꢔꢈꢦꢔꢒꢍꢘꢑꢒꢊꢹꢔꢦꢈꢋꢊꢙꢎꢑꢙꢊꢍꢐꢈꢊꢐꢈꢙꢉꢔꢈꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢊꢐꢧꢈꢄꢸꢂꢁꢈꢚꢍꢏꢈꢙꢉꢔꢈ
ꢔꢽꢊꢋꢈꢋꢙꢏꢎꢘꢙꢎꢏꢔꢈ{ꢐꢂꢉꢟꢈ
ꢀ
ꢫꢡꢬꢈꢮꢍꢐꢦꢠꢈꢑꢧꢑꢊꢐꢈꢊꢐꢈꢑꢧꢏꢔꢔꢛꢔꢐꢙꢈꢽꢊꢙꢉꢈꢙꢉꢔꢈꢩꢏꢍꢩꢍꢋꢔꢦꢈꢔꢐꢔꢣꢑꢛꢊꢦꢍꢈꢸꢔꢽꢊꢋꢈ
ꢀ
ꢸ
ꢋꢙꢏꢎꢘꢙꢎꢏꢔꢟꢈꢷꢉꢔꢐꢈꢔꢞꢙꢔꢐꢦꢔꢦꢈꢙꢍꢈꢜꢣꢫꢑꢏꢖꢒꢔꢙꢉꢖꢐꢖꢒꢬꢩꢖꢏꢊꢦꢊꢐꢔꢈꢦꢔꢏꢊꢭꢑꢙꢊꢭꢔꢋꢠꢈꢊꢐꢈ
ꢽ
ꢉꢊꢘꢉꢈ ꢙꢉꢔꢈ ꢑꢏꢖꢒꢈ ꢎꢐꢊꢙꢈ ꢊꢋꢈ ꢐꢍꢙꢈ ꢩꢖꢏꢊꢦꢊꢐꢔꢣꢦꢔꢏꢊꢭꢔꢦꢠꢈ ꢙꢉꢔꢈ ꢎꢋꢎꢑꢒꢈ ꢋꢖꢐꢙꢉꢔꢙꢊꢘꢈ
ꢇꢉꢊꢋꢈꢌꢍꢎꢏꢐꢑꢒꢈꢊꢋꢈꢓꢈꢇꢉꢔꢈꢕꢍꢖꢑꢒꢈꢗꢍꢘꢊꢔꢙꢖꢈꢍꢚꢈꢀꢉꢔꢛꢊꢋꢙꢏꢖꢈꢜꢝꢞꢞ
Wꢀ bꢁꢂꢃꢟꢠꢈꢜꢝꢡꢢꢠꢈꢈꢈꢠꢈꢡꢣꢢꢈꢤꢈ4ꢈ
ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ

ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ
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DOI: 10.1039/C8CC00478A
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Wꢀꢁꢂꢃꢄꢅ bꢄꢆꢇꢈ
ꢩꢏꢍꢙꢍꢘꢍꢒꢈ ꢧꢑꢭꢔꢈ ꢙꢉꢔꢈ ꢘꢍꢏꢏꢔꢋꢩꢍꢐꢦꢊꢐꢧꢈ ꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢒꢵꢔꢐꢔꢋꢈ ꢊꢐꢋꢙꢔꢑꢦꢈ ꢍꢚꢈ ꢙꢉꢔꢈ ꢘꢑꢏꢮꢍꢛꢔꢙꢑꢒꢒꢑꢙꢊꢍꢐ/ꢔꢒꢔꢘꢙꢏꢍꢩꢉꢊꢒꢊꢘꢈ ꢑꢦꢦꢊꢙꢊꢍꢐꢈ ꢋꢙꢏꢑꢙꢔꢧꢖꢈ ꢘꢍꢛꢛꢍꢐꢒꢖꢈ
ꢡꢡ
ꢔꢞꢩꢔꢘꢙꢔꢦꢈꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢒꢵꢑꢐꢔꢋꢈꢊꢐꢈꢒꢍꢽꢈꢙꢍꢈꢛꢍꢦꢔꢏꢑꢙꢔꢈꢖꢊꢔꢒꢦꢋꢟꢈꢆꢈꢋꢎꢮꢋꢙꢑꢐꢙꢊꢑꢒꢈ ꢎꢋꢔꢦꢈꢚꢍꢏꢈꢙꢉꢔꢈꢡꢠꢜꢣꢚꢎꢐꢘꢙꢊꢍꢐꢑꢒꢊꢹꢑꢙꢊꢍꢐꢈꢍꢚꢈꢑꢒꢵꢖꢐꢔꢋꢟ ꢈ
ꢊꢐꢘꢏꢔꢑꢋꢔꢈ ꢊꢐꢈ ꢙꢉꢔꢈ ꢊꢋꢍꢒꢑꢙꢔꢦꢈ ꢖꢊꢔꢒꢦꢈ ꢽꢑꢋꢈ ꢑꢘꢉꢊꢔꢭꢔꢦꢈ ꢊꢐꢈ ꢩꢏꢔꢋꢔꢐꢘꢔꢈ ꢍꢚꢈ ꢡꢟꣀꢈ
/
ꢀꢃꢕꢅꢑꢍꢐꢌ ꢀꢕ ꢑꢃꢐꢇꢂꢇꢌꢐ
ꢔꣅꢎꢊꢭꢑꢒꢔꢐꢙꢋꢈꢍꢚꢈꢦꢊꢊꢋꢍꢩꢏꢍꢩꢖꢒꢈꢦꢊꢋꢎꢒꢚꢊꢦꢔꢈꢫꢗꢘꢉꢔꢛꢔꢈꣀꢬꢟꢈ
ꢇꢉꢔꢏꢔꢈꢑꢏꢔꢈꢐꢍꢈꢘꢍꢐꢚꢒꢊꢘꢙꢋꢈꢍꢚꢈꢊꢐꢙꢔꢏꢔꢋꢙꢈꢙꢍꢈꢦꢔꢘꢒꢑꢏꢔꢟꢈ
1
2
3
. iPrSSiPr
Ar
Ar
Ar
Ar
. Ti(OiPr)
. ArMgBr
4
bꢀꢐꢇꢌ ꢄꢃꢒ ꢂꢇꢕꢇꢂꢇꢃꢍꢇꢌ
N
N
H
2
O
ꢡꢈꢈꢈꢺꢟꢈꢣꢲꢟꢈꢇꢔꢮꢮꢔꢐꢠꢈꢾꢟꢈ ꢕꢑꢎꢘꢉꢠꢈꢀꢟꢈꢗꢙꢏꢑꢙꢛꢑꢐꢐꢠꢈꢀꢟꢈꢂꢟꢈ ꢷꢊꢒꢒꢊꢑꢛꢋꢈꢑꢐꢦꢈꢆꢟꢈꢦꢔꢈ
ꢂꢔꢊꢌꢔꢏꢔꢠꢈhꢆꢇꢀ [ꢃꢍꢍꢀꢠꢈꢜꢝꢝꢢꢠꢈ
7
ꢠꢈꢿ꣋ꢢ꣆ꢈ꣒ꢟꢈꢣꢲꢟꢈꢷꢎꢈꢑꢐꢦꢈ꣓ꢟꢈ ꢣꣂꢟꢈ꣒ꢎꢠꢈ Wꢀ !ꢂꢀ
ꢋꢃꢂꢀ {ꢅꢊꢀꢠꢈ ꢜꢝꢝꢡꢠꢈꢉ%4ꢠꢈꣀ꣊꣊꣊꣆ꢈ ꢥꢟꢈ ꣈ꢔꢏꢙꢎꢋꢈꢑꢐꢦꢈ ꢴꢟꢈꢗꢹꢖꢛꢍꢐꢊꢑꢵꢠꢈ /ꢋꢃꢂꢀ
ꢅꢂꢂꢎꢄꢀꢠꢈꢜꢝꢝꢡꢠꢈ ꢠꢈꢡ꣊ꢳꢜ꣆ꢈꢼꢟꢈꢀꢉꢑꢩꢒꢊꢐꢋꢵꢊꢈꢑꢐꢦꢈꢆꢟꢈꢦꢔꢈꢂꢔꢊꢌꢔꢏꢔꢠꢈ!ꢄꢇꢃꢙꢀ
ꢋꢃꢂꢀ Lꢄꢍꢀ 9ꢒꢀꢠꢈꢡꢳꢳ꣄ꢠꢈ47ꢠꢈꢿꢡꢢ꣆ꢈꢁꢟꢈꢺꢟꢈꢾꢎꢒꢊꢐꢵꢍꢭꢊꢘꢉꢠꢈꢆꢟꢈꢅꢟꢈꢗꢑꢭꢘꢉꢔꢐꢵꢍꢠꢈꢗꢟꢈ
ꢟꢈꢗꢭꢊꢏꢊꢦꢍꢭꢈꢑꢐꢦꢈꢲꢟꢈꢆꢟꢈꢼꢑꢋꢊꢒꢔꢭꢋꢵꢊꢠꢈaꢃꢄꢒꢃꢓꢃꢃꢐ /ꢅꢂꢂꢎꢄꢀꢠꢈꢡꢳꢳꢢꢠꢈ ꢠꢈꢜꢢꢝ꣆ꢈ
ꢟꢈ ꢺꢟꢈ ꢾꢎꢒꢊꢐꢵꢍꢭꢊꢘꢉꢠꢈ ꢗꢟꢈ ꢼꢟꢈ ꢗꢭꢊꢏꢊꢦꢍꢭꢈ ꢑꢐꢦꢈ ꢲꢟꢈ ꢆꢟꢈ ꢼꢑꢋꢊꢒꢔꢭꢋꢵꢊꢠꢈ {&ꢄꢍꢋꢃꢉꢈꢉꢠꢈ
ꢡꢳꢳꢡꢠꢈ ꢠꢈꢜꢢꢿꢟꢈ
ꢜꢈꢈꢈꢈꢈꢗꢟꢈ ꢁꢵꢑꢛꢍꢙꢍꢠꢈ ꢲꢟꢈ ꢾꢟꢈ ꢆꢐꢈ ꢑꢐꢦꢈ Fꢟꢈ ꢗꢑꢙꢍꢠꢈ Çꢃꢍꢆꢁꢋꢃꢒꢆꢅꢄ [ꢃꢍꢍꢀꢠꢈ ꢡꢳꢳ꣋ꢠꢈ 4:ꢠꢈ
ꣀꣀꢡ꣆ꢈꢶꢟꢈꢃꢏꢑꢮꢔꢠꢈꢇꢟꢈꢇꢑꢵꢔꢦꢑꢠꢈꢲꢟꢈꢶꢊꢦꢔꢎꢏꢑꢈꢑꢐꢦꢈFꢟꢈꢗꢑꢙꢍꢠꢈ Wꢀ !ꢂꢀ /ꢋꢃꢂꢀ
/
/
/
Ph4F
Ph4F
Ph
Ph
Ph
Th
Th
ꢈ
N
N
N
Ph4F
Th
3c, 48-35%
ꢼ
4
ꢁ
3
a, 61-52%
3b, 59-45%
4
Ph
Ph
Ph4F
N
Ph4F
Ph4F
Ph4F
N
Ph4F
Ph4F
ꢿ
N
Ph
{ꢅꢊꢀꢠꢈꢡꢳꢳ꣊ꢠꢈꢉꢉ:ꢠꢈꢡꢡꢜꢳꣀ꣆ꢈꢆꢟꢈꢾꢑꢋꢑꢙꢵꢊꢐꢠꢈꢇꢟꢈꢄꢑꢵꢑꢧꢑꢽꢑꢠꢈꢗꢟꢈꢁꢵꢑꢛꢍꢙꢍꢈꢑꢐꢦꢈ
Fꢟꢈ ꢗꢑꢙꢍꢠꢈ Wꢀ !ꢂꢀ /ꢋꢃꢂꢀ {ꢅꢊꢀꢠꢈ ꢡꢳꢳꣀꢠꢈ ꢉꢉ9ꢠꢈ ꢢ꣋꣋ꢡ꣆ꢈ ꢇꢟꢈ ꢄꢑꢵꢑꢧꢑꢽꢑꢠꢈ ꢆꢟꢈ
N
ꢾ
ꢑꢋꢑꢙꢵꢊꢐꢈꢑꢐꢦꢈFꢟꢈꢗꢑꢙꢍꢠꢈÇꢃꢍꢆꢁꢋꢃꢒꢆꢅꢄ [ꢃꢍꢍꢀꢠꢈꢡꢳꢳꣀꢠꢈ41ꢠꢈꢢꢜꢝ꣊ꢟꢈꢈꢈꢈꢈꢈꢈꢈ
3
d, 40-35%
3e, 63-60%
3f, 60%
ꢢꢈꢈꢈꢗꢟꢈꢁꢵꢑꢛꢍꢙꢍꢠꢈꢂꢟꢈꢅꢽꢑꢵꢎꢮꢍꢠꢈꢾꢟꢈꢾꢍꢮꢑꢖꢑꢋꢉꢊꢈꢑꢐꢦꢈFꢟꢈꢗꢑꢙꢍꢠꢈWꢀ !ꢂꢀ /ꢋꢃꢂꢀ
{ꢅꢊꢀꢠꢈꢡꢳꢳ꣊ꢠꢈꢉꢉ:ꢠꢈ꣄ꢳ꣋ꢿꢟꢈ
Ph
Ph Ph
Ph
Ph
Ph4F
Ph4F Ph4F
N
Ph4F
Ph4F
ꢿ
ꢈꢈꢈꢈꢶꢟꢈꢃꢏꢑꢮꢔꢠꢈꢂꢟꢈꢄꢑꢏꢊꢙꢑꢈꢑꢐꢦꢈFꢟꢈꢗꢑꢙꢍꢠꢈ!ꢄꢇꢃꢙꢀ /ꢋꢃꢂꢀ Lꢄꢍꢀ 9ꢒꢀꢠꢈꢡꢳꢳꢳꢠꢈ4;ꢠꢈ
ꢢꣀꢡ꣄꣆ꢈꢶꢟꢈꢃꢏꢑꢮꢔꢠꢈꢇꢟꢈꢇꢑꢵꢔꢦꢑꢈꢑꢐꢦꢈFꢟꢈꢗꢑꢙꢍꢠꢈÇꢃꢍꢆꢁꢋꢃꢒꢆꢅꢄ [ꢃꢍꢍꢀꢠꢈꢡꢳꢳ꣄ꢠꢈ49ꢠꢈ
ꢡꢜꣀꢢꢟꢈ
N
Ph
Ph4F
3
g, 50%
3h, 46%
ꣀꢈꢈ ꢆꢟꢈ ꢷꢍꢒꢑꢐꢈ ꢑꢐꢦꢈ ꣒ꢟꢈ ꢗꢊꢞꢠꢈ Çꢃꢍꢆꢁꢋꢃꢒꢆꢅꢄꢠꢈ ꢜꢝꢡꢝꢠꢈ 11ꢠꢈ ꢡꣀ꣆ꢈ Fꢟꢈ ꢗꢑꢙꢍꢈ ꢑꢐꢦꢈ ꢗꢟꢈ
ꢵꢑꢛꢍꢙꢍꢠꢈ!ꢒꢐꢀ {&ꢄꢍꢋꢀ /ꢁꢍꢁꢓꢀꢠꢈꢜꢝꢝꢡꢠꢈ4.4ꢠꢈ꣊ꣀꢳ꣆ꢈꢁꢟꢈꢺꢟꢈꢾꢎꢒꢊꢐꢵꢍꢭꢊꢘꢉꢠꢈꢁꢟꢈ
ꢸꢟꢈꢪꢩꢋꢙꢔꢊꢐꢠꢈꢼꢟꢈꢪꢟꢈꢅꢋꢑꢵꢍꢭꢈꢑꢐꢦꢈꢪꢟꢈꢆꢟꢈꢾꢉꢛꢔꢒ꣔ꢐꢊꢙꢋꢵꢑꢖꢑꢠꢈ{&ꢄꢓꢃꢍꢍꢀꢠꢈꢜꢝꢝꢡꢠꢈ ꢠꢈ
ꢿꢳ꣆ꢈ ꢁꢟꢈ ꢺꢟꢈꢾꢎꢒꢊꢐꢵꢍꢭꢊꢘꢉꢈ ꢑꢐꢦꢈ ꢆꢟꢈ ꢦꢔꢈ ꢂꢔꢊꢌꢔꢏꢔꢠꢈ /ꢋꢃꢂꢀ wꢃꢐꢀꢠꢈ ꢜꢝꢝꢝꢠꢈꢉꢈꢈꢠꢈ
ꢜ꣊꣋ꢳ꣆ꢈFꢟꢈꢗꢑꢙꢍꢠꢈꢶꢟꢈꢃꢏꢑꢮꢔꢈꢑꢐꢦꢈꢗꢟꢈꢁꢵꢑꢛꢍꢙꢍꢠꢈ{&ꢄꢓꢃꢍꢍꢀꢠꢈꢜꢝꢝꢝꢠꢈ ꢠꢈ꣊ꣀꢢ꣆ꢈFꢟꢈ
ꢁ
ꢈ
{
ꢍꢓꢇꢆꢇ 7ꢈ ꢇꢊꢫꢁꢈꢥꢏꢬ
ꢦꢔꢏꢊꢭꢑꢙꢊꢭꢔꢋꢈ ꢑꢐꢦꢈ ꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢼꢣꢋꢉꢑꢩꢔꢦꢈ ꢜꢠ꣄ꢣꢮꢊꢋꢫꢑꢏꢖꢒꢔꢙꢉꢖꢐꢖꢒꢬꢣ
ꢩꢖꢏꢊꢦꢊꢐꢔꢋꢟꢈꢥꢉꢿFꢈ꣇ꢈꢿꢣFꢣꢀ ꢣꢠꢈꢇꢉꢈ꣇ꢈꢜꢣꢙꢉꢊꢔꢐꢖꢒꢟꢈꢈꢥꢏꢗꢗꢈꢥꢏꢯꢈꢡꢟꣀꢈꢔꣅꢎꢊꢭꢈꢫ4ꢄ&ꢕꢬꢈꢍꢏꢈ
ꢢꢟꢝꢈꢔꣅꢎꢊꢭꢈꢫ4ꢎ* ꢓꢬꢠꢈꣀꢈꢛꢊꢐꢠꢈꢕꢇꢟꢈꢇꢊꢫꢁꢈꢥꢏꢬ ꢯꢈꢉꢋꢈ ꢇ8ꢁꢑ) ꢈꢋꢉ&ꢈꢋ% ꢇ8ꢁꢑ)ꢠꢈꣀꢈꢛꢊꢐꢠꢈ
ꢕꢇꢟꢈ ꢆꢏꢂꢧ꣈ꢏꢯꢈ ꢜꢟꣀꢈ ꢔꣅꢎꢊꢭꢈ ꢫ4ꢄ&ꢕꢬꢈ ꢍꢏꢈ ꣀꢟꢝꢈ ꢔꣅꢎꢊꢭꢈ ꢫ4ꢎ* ꢓꢬꢠꢈ ꣉꣊꣋꣌ꢀꢈ ꢦꢎꢏꢊꢐꢧꢈ ꢙꢉꢔꢈ
ꢿ
ꢣꢛꢔꢦꢊꢑꢙꢔꢦꢈ ꢦꢊꢑꢏꢖꢒꢑꢙꢊꢍꢐꢈ ꢍꢚꢈ ꢜꢣꢫꢑꢏꢖꢒꢔꢙꢉꢖꢐꢖꢒꢬꢩꢖꢏꢊꢦꢊꢐꢔꢈ
ꢉ
꣄
ꢶ
ꢿ
1
ꢿ
/
ꢗꢑꢙꢍꢠꢈꢶꢟꢈꢃꢏꢑꢮꢔꢈꢑꢐꢦꢈꢗꢟꢈꢁꢵꢑꢛꢍꢙꢍꢠꢈ /ꢋꢃꢂꢀ wꢃꢐꢀꢠꢈꢜꢝꢝꢝꢠꢈꢉꢈꢈꢠꢈꢜ꣋ꢢꣀ꣆ꢈꢕꢟꢈ
ꢂꢊꢹꢍꢌꢊꢏꢊꢠꢈꢶꢟꢈꢃꢏꢑꢮꢔꢈꢑꢐꢦꢈFꢟꢈꢗꢑꢙꢍꢠꢈWꢀ hꢆꢇꢀ /ꢋꢃꢂꢀꢠꢈꢜꢝꢝꢝꢠꢈ17ꢠꢈ꣄ꢜꢡ꣊꣆ꢈꢁꢟꢈꢺꢟꢈ
ꢑꢦꢦꢊꢙꢊꢍꢐꢈꢙꢉꢔꢐꢈꢿꢝ꣌ꢀꢠꢈꢉ&4 ꢒꢄꢖꢌ/9 ꢒꢄꢖꢌꢟꢈ
ꢾ
ꢎꢒꢊꢐꢵꢍꢭꢊꢘꢉꢠꢈtꢎꢆꢃ !**ꢓꢀ /ꢋꢃꢂꢀꢠ ꢜꢝꢝꢝꢠꢈ9%ꢠꢈꢡ꣊ꢡꣀ꣆ꢈꢾꢟꢈꢶꢑꢏꢑꢦꢑꢠꢈꢶꢟꢈꢃꢏꢑꢮꢔꢈ
ꢈ
ꢑꢐꢦꢈFꢟꢈꢗꢑꢙꢍꢠꢈÇꢃꢍꢆꢁꢋꢃꢒꢆꢅꢄ [ꢃꢍꢍꢀꢠꢈꢡꢳꢳꣀꢠꢈ41ꢠꢈꢢꢜꢝꢢꢟꢈ
ꢈ
ꢇꢉꢔꢈꢩꢏꢔꢋꢔꢐꢘꢔꢈꢍꢚꢈꢡꢟꣀꢈꢔꣅꢎꢊꢭꢑꢒꢔꢐꢙꢋꢈꢍꢚꢈꢙꢉꢔꢈꢛꢊꢒꢦꢈꢍꢞꢊꢦꢊꢹꢊꢐꢧꢈꢑꢧꢔꢐꢙꢈ
ꢊꢋꢍꢩꢏꢍꢩꢖꢒꢈ ꢦꢊꢋꢎꢒꢚꢊꢦꢔꢠꢈ ꢏꢔꢩꢒꢑꢘꢊꢐꢧꢈ ꢙꢉꢔꢈ ꢅ ꢈ ꢔꢛꢩꢒꢍꢖꢔꢦꢈ ꢊꢐꢈ ꢋꢙꢔꢩꢈ Lëꢈ ꢊꢐꢈ
ꢗꢘꢉꢔꢛꢔꢈ ꢢꢠꢈ ꢑꢒꢒꢍꢽꢔꢦꢈ ꢚꢍꢏꢈ ꢙꢉꢔꢈ ꢎꢋꢔꢈ ꢍꢚꢈ ꢑꢈ ꢘꢑꢙꢑꢒꢖꢙꢊꢘꢈ ꢑꢛꢍꢎꢐꢙꢈ ꢍꢚꢈ ꣊ꢈ ꢸꢟꢈ ꢲꢟꢈ ꢲꢎꢏꢚꢔꢔꢠꢈ ꢴꢟꢈ ꢪꢟꢈ ꢶꢊꢒꢒꢠꢈ ꢥꢟꢈ ꢪꢟꢈ Fꢑꢐꢽꢊꢘꢵꢈ ꢑꢐꢦꢈ ꢅꢟꢈ ꢥꢟꢈ ꢕꢍꢙꢉꢽꢔꢒꢒꢠꢈ
ꢇꢊꢫꢁꢈꢥꢏꢬ ꢈꢫꢡꢝꢣꢜꢝꢈꢛꢍꢒꢣ꣎ꢬꢠꢈꢽꢊꢙꢉꢈꢘꢍꢛꢩꢑꢏꢑꢮꢒꢔꢈꢊꢋꢍꢒꢑꢙꢔꢦꢈꢖꢊꢔꢒꢦꢋꢈꢮꢎꢙꢈꢑꢈ
hꢆꢇꢁꢄꢅꢂꢃꢍꢁꢓꢓꢈꢊꢉꢠꢈ ꢡꢳꢳꢝꢠꢈ ꢠꢈ ꣊ꣀ꣆ꢈ ꢂꢟꢈ ꢺꢟꢈ ꢇꢉꢍꢏꢐꢠꢈ ꢴꢟꢈ ꢪꢟꢈ ꢶꢊꢒꢒꢠꢈ ꢗꢟꢈ ꢆꢟꢈ
꣄
ꢈꢈ ꢇꢟꢈꢕꢍꢙꢉꢠꢈꢶꢟꢈꢷꢑꢦꢔꢩꢍꢉꢒꢠꢈꢪꢟꢈꢀꢒꢍꢙꢈꢑꢐꢦꢈꢸꢟꢈꢶꢟꢈꢺꢑꢦꢔꢠꢈ/ꢋꢃꢂꢀ 9ꢎꢆꢀ Wꢀꢠꢈꢜꢝꢡꣀꢠꢈ
ꢜ
%ꢉꢠꢈꢡ꣋꣊ꢢꢝꢟꢈ
ꢿ
:
ꢋꢒꢍꢽꢔꢏꢈ ꢩꢏꢍꢦꢎꢘꢙꢈ ꢧꢔꢐꢔꢏꢑꢙꢊꢍꢐꢟꢈ ꢇꢉꢔꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢈ
ꢷꢑꢏꢑꢙꢎꢵꢔꢠꢈꢪꢟꢈꢗꢟꢈꢴꢍꢉꢐꢋꢍꢐꢠꢈꢥꢟꢈꢪꢟꢈFꢑꢐꢽꢊꢘꢵꢈꢑꢐꢦꢈꢅꢟꢈ ꢥꢟꢈ ꢕꢍꢙꢉꢽꢔꢒꢒꢠꢈ Wꢀ !ꢂꢀ
/ꢋꢃꢂꢀ {ꢅꢊꢀꢠꢈꢡꢳꢳ꣊ꢠꢈꢉꢉ:ꢠꢈ꣋꣄ꢢꢝ꣆ꢈꢂꢟꢈꢲꢟꢈꢗꢩꢔꢐꢘꢔꢏꢠꢈꢗꢟꢈꢕꢟꢈꢷꢊꢒꢋꢍꢐꢈꢑꢐꢦꢈꢺꢟꢈꢗꢟꢈ
ꢊꢐꢙꢔꢏꢛꢔꢦꢊꢑꢙꢔꢈÇꢑ&ꢀꢕꢈꢛꢑꢖꢈꢮꢔꢈꢭꢊꢔꢽꢔꢦꢈꢑꢋꢈꢑꢈꣃꢛꢑꢋꢵꢔꢦꣃꢈꢇꢊꢫꢅꢅꢬꢣꢍꢒꢔꢚꢊꢐꢔꢈ
ꢺ
ꢊꢏꢍꢒꢑꢛꢊꢠꢈ hꢆꢇꢁꢄꢅꢂꢃꢍꢁꢓꢓꢈꢊꢉꢠꢈ ꢡꢳꢳ꣊ꢠꢈ ꢉ1ꢠꢈ ꢢꢝꣀꣀ꣆ꢈ ꢴꢟꢈ ꢾꢟꢈ ꢗꢔꢑꢮꢎꢏꢧꢠꢈ ꢥꢟꢈ ꢴꢟꢈ
π
ꢍꢞꢊꢦꢑꢙꢊꢭꢔꢈꢑꢦꢦꢊꢙꢊꢍꢐꢈꢑꢙꢈꢇꢊꢫꢅꢅꢬꢈꢘꢔꢐꢙꢔꢏꢋꢈꢊꢋꢈꢵꢐꢍꢽꢐꢈꢏꢔꢑꢘꢙꢊꢭꢔꢈꢩꢑꢙꢙꢔꢏꢐꢟ ꢈ
ꢣꢘꢍꢛꢩꢒꢔꢞꢠꢈ ꢑꢐꢦꢈ ꢙꢉꢔꢈ ꢑꢮꢊꢒꢊꢙꢖꢈ ꢍꢚꢈ ꢑꢒꢵꢖꢒꢈ ꢦꢊꢋꢎꢒꢚꢊꢦꢔꢋꢈ ꢙꢍꢈ ꢎꢐꢦꢔꢏꢧꢍꢈ
꣋
Fꢊꢋꢘꢉꢔꢏꢠꢈꢼꢟꢈꢺꢟꢈ꣒ꢍꢎꢐꢧꢈꢴꢎꢐꢊꢍꢏꢈꢑꢐꢦꢈꢴꢟꢈꢪꢟꢈꢪꢒꢒꢊꢋꢠꢈ !ꢄꢇꢃꢙꢀ /ꢋꢃꢂꢀ Lꢄꢍꢀ 9ꢒꢀꢠꢈ
ꢡꢳꢳ꣋ꢠꢈ49ꢠꢈꢡꣀꣀ꣆ꢈꢾꢟꢈꢆꢟꢈꢆꢮꢮꢍꢎꢦꢠꢈꢥꢟꢈꢄꢟꢈꢄꢊꢘꢵꢊꢑꢋꢈꢑꢐꢦꢈꢪꢟꢈ꣒ꢟꢈꢣꣂꢟꢈꢀꢉꢔꢐꢠꢈ!ꢊꢍꢁ
ꢇꢉꢔꢈꢏꢔꢋꢎꢒꢙꢊꢐꢧꢈꢮꢊꢋꢫꢊꢋꢍꢩꢏꢍꢩꢖꢒꢋꢎꢒꢚꢊꢦꢍꢬꢈꢋꢩꢔꢘꢊꢔꢋꢈꢙꢉꢔꢐꢈꢏꢔꢑꢘꢙꢋꢈꢽꢊꢙꢉꢈꢙꢉꢔꢈ
/
ꢆ&ꢉꢍꢀꢠꢈ ꢜꢝꢝꢡꢠꢈ /79ꢠꢈ ꢡꢿꢝ꣋꣆ꢈ ꢴꢟꢈꢗꢙꢏꢍꢍꢙꢠꢈꢆꢟꢈꢸ꣕ꢙꢹꢔꢐꢠꢈ ꢂꢟꢈFꢏꢊꢔꢦꢔꢛꢑꢐꢐꢠꢈ ꢷꢟꢈ
ꢗꢑꢑꢵꢈꢑꢐꢦꢈꢕꢟꢈ꣈ꢔꢘꢵꢉꢑꢎꢋꢠꢈùꢀ !ꢄꢅꢆꢇꢀ !ꢓꢓꢇꢀ /ꢋꢃꢂꢀꢠꢈꢜꢝꢝꢜꢠꢈ1%;ꢠꢈ꣊ꢳ꣊꣆ꢈ꣈ꢟꢈꢺꢟꢈ
ꢑꢏꢭꢔꢖꢠꢈꢆꢟꢈꢂꢟꢈꢆꢏꢊꢚꢈꢑꢐꢦꢈꢕꢟꢈꢲꢟꢈꢪꢏꢐꢋꢙꢠꢈWꢀ /ꢋꢃꢂꢀ /ꢆ&ꢉꢍꢁꢓꢓꢅꢇꢆꢀꢠꢈꢜꢝꢡꢝꢠꢈ.ꢈꢠꢈ
꣋ꢢꢟꢈ
ꢺ
ꢏꢊꢧꢐꢑꢏꢦꢈ ꢏꢔꢑꢧꢔꢐꢙꢈ ꢑꢐꢦꢈ ꢙꢉꢔꢈ ꢑꢒꢵꢖꢐꢖꢒꢩꢖꢏꢊꢦꢊꢐꢔꢈ ꢋꢎꢮꢋꢙꢏꢑꢙꢔꢈ ꢙꢍꢈ
ꢏꢔꢧꢔꢐꢔꢏꢑꢙꢔꢈÇꢑ&ꢀꢕꢟꢈꢇꢉꢊꢋꢈꢩꢏꢍꢙꢍꢘꢍꢒꢈꢽꢑꢋꢈꢋꢎꢘꢘꢔꢋꢋꢚꢎꢒꢒꢖꢈꢔꢞꢙꢔꢐꢦꢔꢦꢈꢙꢍꢈꢼꢣ
ꢋꢉꢑꢩꢔꢦꢈ ꢜꢠ꣄ꢣꢮꢊꢋꢫꢑꢏꢖꢒꢔꢙꢉꢖꢐꢖꢒꢬꢩꢖꢏꢊꢦꢊꢐꢔꢋꢠꢈꢧꢊꢭꢊꢐꢧꢈꢙꢉꢔꢈ ꢔꢞꢩꢔꢘꢙꢔꢦꢈ ꢜꢠ꣄ꢣ
ꢮꢊꢋꢫꢡꢠꢜꢠꢜꢣꢙꢏꢊꢑꢏꢖꢒꢭꢊꢐꢖꢒꢬꢩꢖꢏꢊꢦꢊꢐꢔꢋꢈ 4ꢎ ꢑꢐꢦ 4ꢓꢈ ꢑꢋꢈ ꢙꢉꢔꢈ ꢏꢔꢋꢩꢔꢘꢙꢊꢭꢔꢈ
ꢙꢔꢙꢏꢑꢑꢏꢖꢒꢑꢙꢊꢍꢐꢈ ꢩꢏꢍꢦꢎꢘꢙꢋꢟꢈ ꢇꢉꢔꢈ ꢚꢑꢘꢊꢒꢔꢈ ꢑꢘꢘꢔꢋꢋꢈ ꢙꢍꢈ ꢋꢎꢘꢉꢈ ꢙꢑꢏꢧꢔꢙꢈ
ꢶ
꣊
꣋
ꢈꢈ ꢺꢟꢈFꢑꢘꢉꢊꢐꢔꢙꢙꢊꢈꢑꢐꢦꢈꢀꢟꢈFꢒꢍꢏꢊꢑꢐꢊꢠꢈWꢀ /ꢋꢃꢂꢀ {ꢅꢊꢀꢏ ꢚꢁꢓꢍꢅꢄ Çꢆꢁꢄꢉꢀꢠꢈꢡꢳ꣊ꢿꢠꢈꢈꢠꢈ
ꢜꢿꢢꢢꢟꢈ
ꢘꢍꢛꢩꢍꢎꢐꢦꢋꢈꢊꢋꢈꢍꢚꢈꢩꢑꢏꢙꢊꢘꢎꢒꢑꢏꢈꢊꢐꢙꢔꢏꢔꢋꢙꢈꢦꢎꢔꢈꢙꢍꢈꢙꢉꢔꢊꢏꢈꢩꢏꢍꢩꢔꢏꢙꢊꢔꢋꢈꢑꢋꢈ ꢳꢈꢈ ꢲꢟꢈꢴꢑꢐꢑꢈꢑꢐꢦꢈ꣈ꢟꢈꢾꢟꢈꢺꢉꢍꢏꢑꢊꢠꢈÇꢃꢍꢆꢁꢋꢃꢒꢆꢅꢄꢠꢈꢜꢝꢡꢜꢠꢈ1;ꢠꢈ꣊ꢢꢝꢳꢟꢈ
ꢚꢒꢎꢍꢏꢍꢩꢉꢍꢏꢋꢠꢈꢑꢋꢈꢉꢑꢭꢔꢈꢮꢔꢔꢐꢈꢏꢔꢘꢔꢐꢙꢒꢖꢈꢏꢔꢩꢍꢏꢙꢔꢦꢈꢚꢍꢏꢈ4ꢎꢈꢑꢐꢦꢈꢏꢔꢒꢑꢙꢔꢦꢈ ꢡꢝꢈꢈ ꢂꢟꢈꢇꢟꢈꢺꢑꢮꢏꢈꢑꢐꢦꢈFꢟꢈꢀꢟꢈꢥꢊꢧꢧꢔꢠꢈw{/ !ꢒꢐꢀꢠꢈꢜꢝꢡꣀꢠꢈ ꢠꢈꢳꢝꢜꢜ꣄ꢟꢈꢈ
7
ꢳ
ꢛꢔꢙꢑꢣꢮꢏꢑꢐꢘꢉꢔꢦꢈ ꢜꢠ꣄ꢣꢮꢊꢋꢫꢡꢠꢜꢠꢜꢣꢙꢏꢊꢑꢏꢖꢒꢭꢊꢐꢖꢒꢬꢩꢖꢏꢊꢦꢊꢐꢔꢋ ꢈ ꢑꢋꢈ ꢽꢔꢒꢒꢈ ꢑꢋꢈ ꢡꢡꢈꢈ ꢪꢟꢈ ꢴꢟꢈ ꢀꢍꢏꢔꢖꢈ ꢑꢐꢦꢈ ꢴꢟꢈ ꢆꢟꢈ ꢾꢑꢙꢹꢔꢐꢔꢒꢒꢔꢐꢮꢍꢧꢔꢐꢠꢈ Wꢀ !ꢂꢀ /ꢋꢃꢂꢀ {ꢅꢊꢀꢠꢈ ꢡꢳ꣄ꢳꢠꢈ :ꢉꢠꢈ
ꢡꢝ
ꢡ꣋ꣀꢡ꣆ꢈꢾꢟꢈꢶꢟꢈꢀꢉꢎꢈꢑꢐꢦꢈꢾꢟꢈꢾꢟꢈꢷꢑꢐꢧꢠꢈWꢀ hꢆꢇꢀ /ꢋꢃꢂꢀꢠꢈꢡꢳ꣋꣄ꢠꢈ7ꢉꢠꢈ꣊꣄꣊꣆ꢈꢗꢟꢈꢆꢟꢈꢕꢑꢍꢈ
4"
ꢟꢈ
ꢑꢐꢦꢈꢥꢟꢈꢾꢐꢍꢘꢉꢔꢒꢠꢈWꢀ !ꢂꢀ /ꢋꢃꢂꢀ {ꢅꢊꢀꢠꢈꢡꢳꢳꢡꢠꢈꢉꢉ4ꢠꢈꣀ꣊ꢢꣀ꣆ꢈꢇꢟꢈꢗꢙ꣕ꢦꢔꢛꢑꢐꢐꢠꢈꢂꢟꢈ
ꢅꢮꢏꢑꢉꢊꢛꢣꢁꢎꢑꢒꢊꢈꢑꢐꢦꢈꢥꢟꢈꢾꢐꢍꢘꢉꢔꢒꢈÇꢃꢍꢆꢁꢋꢃꢒꢆꢅꢄꢠꢈꢡꢳꢳ꣋ꢠꢈ7.ꢠꢈꢡꢜꢳꢳ꣆ꢈꢄꢟꢈ꣓ꢉꢎꢈꢑꢐꢦꢈ
ꢲꢟꢈꢺꢟꢈꢶꢑꢒꢒꢠꢈWꢀ hꢆꢇꢀ /ꢋꢃꢂꢀꢈꢜꢝꢝꢢꢠꢈ1;ꢠꢈ꣄ꢝ꣄꣄꣆ꢈꢄꢟꢈFꢟꢈꢂꢘꢾꢊꢐꢒꢔꢖꢈꢑꢐꢦꢈꢲꢟꢈFꢟꢈꢁ꣖ꢗꢉꢔꢑꢠꢈ
Wꢀ hꢆꢇꢀ /ꢋꢃꢂꢀꢠꢈꢜꢝꢝ꣄ꢠꢈ9ꢉꢠꢈꢳꣀꣀꢜ꣆ꢈFꢟꢈꣂꢎꢔꢠꢈꢴꢟꢈ꣓ꢉꢑꢍꢠꢈꢇꢟꢈꢗꢟꢈꢆꢟꢈꢶꢍꢏꢈꢑꢐꢦꢈꢇꢟꢈꢶꢑꢖꢑꢋꢉꢊꢠꢈ
Wꢀ !ꢂꢀ /ꢋꢃꢂꢀ {ꢅꢊꢀꢠꢈꢜꢝꢡꣀꢠꢈꢉ49ꢠꢈꢢꢡ꣋ꢳ꣆ꢈꢲꢟꢈꢗꢟꢈꢂ꣕ꢒꢒꢔꢏꢈꢑꢐꢦꢈꢅꢟꢈꢂꢑꢏꢔꢵꢠꢈ/ꢋꢃꢂꢀ
ꢈ
ꢅꢐꢈ ꢘꢍꢐꢘꢒꢎꢋꢊꢍꢐꢠꢈ ꢑꢈ ꢙꢊꢙꢑꢐꢑꢘꢖꢘꢒꢍꢩꢏꢍꢩꢑꢐꢔꢣꢮꢑꢋꢔꢦꢈ ꢘꢍꢛꢩꢒꢔꢞꢈ ꢉꢑꢋꢈ
ꢮꢔꢔꢐꢈ ꢘꢉꢑꢏꢑꢘꢙꢔꢏꢊꢹꢔꢦꢈ ꢑꢋꢈ ꢑꢈ ꢵꢔꢖꢈ ꢏꢔꢑꢘꢙꢊꢍꢐꢈ ꢊꢐꢙꢔꢏꢛꢔꢦꢊꢑꢙꢔꢈ ꢊꢐꢈ ꢙꢉꢔꢈ
ꢋꢖꢐꢙꢉꢔꢋꢊꢋꢈꢍꢚꢈꢑꢈꢭꢑꢏꢊꢔꢙꢖꢈꢍꢚꢈꢦꢊꢑꢏꢖꢒꢑꢙꢔꢦꢈꢡꢠꢜꢣꢦꢊꢫꢩꢖꢏꢊꢦꢊꢐꢣꢜꢣꢖꢒꢬꢔꢙꢉꢑꢐꢔꢋꢠꢈ
ꢜꢣꢫꢡꢠꢜꢠꢜꢣꢙꢏꢊꢑꢏꢖꢒꢭꢊꢐꢖꢒꢬꢩꢖꢏꢊꢦꢊꢐꢔꢋꢈ ꢑꢐꢦꢈ ꢦꢔꢏꢊꢭꢑꢙꢊꢭꢔꢋꢠꢈ ꢑꢒꢍꢐꢧꢈ ꢽꢊꢙꢉꢈ ꢼꢣ
ꢋꢉꢑꢩꢔꢦꢈ ꢜꢠ꣄ꢣꢮꢊꢋꢫꢡꢠꢜꢠꢜꢣꢙꢏꢊꢑꢏꢖꢒꢭꢊꢐꢖꢒꢬꢩꢖꢏꢊꢦꢊꢐꢔꢋꢟꢈ ꢇꢉꢔꢈ ꢦꢍꢎꢮꢒꢔꢈ
ꢐꢎꢘꢒꢔꢍꢩꢉꢊꢒꢊꢘꢈꢑꢦꢦꢊꢙꢊꢍꢐꢈꢙꢍꢈꢩꢖꢏꢊꢦꢖꢒꢑꢒꢵꢖꢐꢔꢋꢈꢦꢔꢋꢘꢏꢊꢮꢔꢦꢈꢊꢐꢈꢙꢉꢊꢋꢈꢽꢍꢏꢵꢈ
ꢏꢔꢩꢏꢔꢋꢔꢐꢙꢋꢈ ꢑꢈ ꢐꢔꢽꢈ ꢏꢔꢑꢘꢙꢊꢭꢊꢙꢖꢈ ꢩꢑꢙꢙꢔꢏꢐꢈ ꢘꢍꢛꢩꢒꢔꢛꢔꢐꢙꢊꢐꢧꢈ ꢙꢉꢔꢈ
{ꢅꢊꢀ wꢃꢐꢀꢠꢈꢜꢝꢡ꣄ꢠꢈ.7ꢠꢈꢿꣀꣀꢜꢟꢈ
.
ꢈꢤꢈWꢀ bꢁꢂꢃꢟꢠꢈꢜꢝꢡꢜꢠꢈꢈꢈꢠꢈꢡꢣꢢꢈ
ꢇꢉꢊꢋꢈꢌꢍꢎꢏꢐꢑꢒꢈꢊꢋꢈꢓꢈꢇꢉꢔꢈꢕꢍꢖꢑꢒꢈꢗꢍꢘꢊꢔꢙꢖꢈꢍꢚꢈꢀꢉꢔꢛꢊꢋꢙꢏꢖꢈꢜꢝꢞꢞꢈ
ꢥꢒꢔꢑꢋꢔꢈꢦꢍꢈꢐꢍꢙꢈꢑꢦꢌꢎꢋꢙꢈꢛꢑꢏꢧꢊꢐꢋꢈ

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ChemComm
View Article Online
DOI: 10.1039/C8CC00478A