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78649874954
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See Supporting Information for bond enthalpy calculations
-
See Supporting Information for bond enthalpy calculations.
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114
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78649844826
-
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Attempts to insert unactivated olefins into Ln-SR and An-SR bonds have thus far been unsuccessful
-
Attempts to insert unactivated olefins into Ln-SR and An-SR bonds have thus far been unsuccessful.
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115
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78649849814
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See Supporting Information for bond enthalpy calculations
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See Supporting Information for bond enthalpy calculations.
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0002388423
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Fiandanese, V.; Marchese, G.; Naso, F.; Ronzini, L. Synthesis 1987, 1034-1036
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Fiandanese, V.1
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127
-
-
78649833870
-
-
Similar attempts with stirring show drastically reduced conversion, possibly the result of accelerated catalyst aggregation
-
Similar attempts with stirring show drastically reduced conversion, possibly the result of accelerated catalyst aggregation.
-
-
-
-
128
-
-
78649881308
-
-
note
-
Alkyne dimers are not observed in NMR-scale reactions. The presence of the small quantities of dimer early in the preparative scale likely results from 5 -mediated dimerization of 1-hexyne before the benzylmercaptan thaws.
-
-
-
-
129
-
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29944446490
-
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Komeyama, K.1
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Takehira, K.4
Takaki, K.5
-
130
-
-
78649805037
-
-
Precipitate colors vary as a function of lanthanide. See Supporting Information
-
Precipitate colors vary as a function of lanthanide. See Supporting Information.
-
-
-
-
131
-
-
0008722332
-
-
Zhang, L.-X.; Zhou, X.-G.; Huang, Z.-E.; Cai, R.-F.; Huang, X.-Y. Polyhedron 1999, 18, 1533-1537
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0001959827
-
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Mashima, K.; Nakayama, Y.; Shibahara, T.; Fukumoto, H.; Nakamura, A. Inorg. Chem. 1996, 35, 93-99
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-
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Mashima, K.1
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Fukumoto, H.4
Nakamura, A.5
-
133
-
-
78649862168
-
-
It is unclear if this Markovnikov hydrothiolation activity is the result of the heterogeneous species exhibiting hydrothiolation activity or if it results from traces of homogeneous catalyst still remaining in solution
-
It is unclear if this Markovnikov hydrothiolation activity is the result of the heterogeneous species exhibiting hydrothiolation activity or if it results from traces of homogeneous catalyst still remaining in solution.
-
-
-
-
136
-
-
78649815927
-
-
The turnover frequency for complex 1 was unobtainable due to heavy precipitate formation immediately after addition of excess thiol
-
The turnover frequency for complex 1 was unobtainable due to heavy precipitate formation immediately after addition of excess thiol.
-
-
-
-
137
-
-
78649889484
-
-
6
-
6.
-
-
-
-
138
-
-
78649843790
-
-
No NMR data on ring cleavage rates for complex 4 were obtainable due to large quantities of precipitation in the NMR tube
-
No NMR data on ring cleavage rates for complex 4 were obtainable due to large quantities of precipitation in the NMR tube.
-
-
-
-
139
-
-
78649834829
-
-
Images of the resulting precipitates are provided in the Supporting Information
-
Images of the resulting precipitates are provided in the Supporting Information.
-
-
-
-
140
-
-
78649825158
-
-
Unfortunately, due to rapid catalyst precipitation, turnover frequencies could not be accurately measured for most thiols and alkynes, preventing quantitative comparison of substrate hydrothiolation activity
-
Unfortunately, due to rapid catalyst precipitation, turnover frequencies could not be accurately measured for most thiols and alkynes, preventing quantitative comparison of substrate hydrothiolation activity.
-
-
-
-
141
-
-
78649877180
-
-
Additional internal alkyne and terminal α-trisubstituted alkynes were surveyed and displayed little or no activity
-
Additional internal alkyne and terminal α-trisubstituted alkynes were surveyed and displayed little or no activity.
-
-
-
-
142
-
-
0001303851
-
-
Bordwell, F. G.; Zhang, X.-M.; Satish, A. V.; Cheng, J. P. J. Am. Chem. Soc. 1994, 116, 6605-6610
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-
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0000088244
-
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Janousek, B. K.; Reed, K. J.; Brauman, J. I. J. Am. Chem. Soc. 1980, 102, 3125-3129
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1642391910
-
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Kreevoy, M. M.; Harper, E. T.; Duvall, R. E.; Wilgus, H. S.; Ditsch, L. T. J. Am. Chem. Soc. 1960, 82, 4899-4902
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-
147
-
-
78649846880
-
-
A plot of ln(rate) vs ln([catalyst]) does not give a linear trend, furthur demonstrating that the hydrothiolation reaction is not second-order with respect to [catalyst]
-
A plot of ln(rate) vs ln([catalyst]) does not give a linear trend, furthur demonstrating that the hydrothiolation reaction is not second-order with respect to [catalyst].
-
-
-
-
149
-
-
78649827240
-
-
Large excesses of alkyne are found to delay precipitate formation
-
Large excesses of alkyne are found to delay precipitate formation.
-
-
-
-
150
-
-
78649826704
-
-
2 is observed, it can be estimated that thiol-mediated protonolysis is >50× faster than analogous alkyne-mediated protonolysis
-
2 is observed, it can be estimated that thiol-mediated protonolysis is >50× faster than analogous alkyne-mediated protonolysis.
-
-
-
-
151
-
-
78649892395
-
-
tBuSH resonance (1.6 ppm)
-
tBuSH resonance (1.6 ppm).
-
-
-
-
152
-
-
78649873412
-
-
note
-
2An< complexes is observed occurring at approximately the same rate. Meanwhile, a comparison of Cp* ring cleavage from complexes 34 and 35 evidences ring cleavage from U at approximately 1/4 the rate observed for Th.
-
-
-
-
155
-
-
78649875430
-
-
Rate measured as beginning of reaction before signifigant ligand protonolysis
-
Rate measured as beginning of reaction before signifigant ligand protonolysis.
-
-
-
-
156
-
-
33746018709
-
-
Roger, M.; Barros, N.; Arliguie, T.; Thuéry, P.; Maron, L.; Ephritikhine, M. J. Am. Chem. Soc. 2006, 128, 8790-8802
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Ephritikhine, M.6
-
157
-
-
78649810062
-
-
Cp-based zirconium complexes are not observed to form insoluable aggregates except at extremely high thiol concentrations, exceeding 1 M, and after extended heating. Despite the observed aggregation, no ligand cleavage is observed
-
Cp-based zirconium complexes are not observed to form insoluable aggregates except at extremely high thiol concentrations, exceeding 1 M, and after extended heating. Despite the observed aggregation, no ligand cleavage is observed.
-
-
-
-
158
-
-
74549141731
-
-
Krogh-Jespersen, K.; Romanelli, M. D.; Melman, J. H.; Emge, T. J.; Brennan, J. G. Inorg. Chem. 2009, 49, 552-560
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Control experiments performed without catalyst evidence the formation of free radical-derived anti-Markonikov products under reaction conditions presented in this study
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The radical inhibitor is added in a 1:1 molar ratio with alkyne
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As is discussed earlier, Markovnikov selectivity is suggestive of alkyne insertion into the M-SR bond
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As is discussed earlier, Markovnikov selectivity is suggestive of alkyne insertion into the M-SR bond.
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