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0345533282
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note
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Test calculations run with both larger basis sets (ADF basis sets IV and V on the ligands) and the PW91 and BLYP functionals gave no significant computed geometrical changes. Further calculations showed the orientation of the OMe ligand does not effect the O-Me bond length.
-
-
-
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67
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0344671006
-
-
note
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2 occurred with minimal activation barriers.
-
-
-
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69
-
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0345533281
-
-
note
-
2 would lead to methoxycarbonyl formation via TS-2a(O), but starting from the cis isomer would favor acyl formation via 2b-TS(C).
-
-
-
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70
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0001752768
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-
Cambridge Structural Database
-
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Allen, F.H.1
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71
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0000016277
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Bruno, I. J.; Cole, J. C.; Edgington, P. R.; Kessler, M.; Macrae, C. F.; McCabe, P.; Pearson, J.; Taylor, R. Acta Crystallogr. 2002, B58, 389.
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Mccabe, P.6
Pearson, J.7
Taylor, R.8
-
72
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0345101843
-
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note
-
2. Cartesian coordinates for 2b(Pd/Pt)-TS(C) and 2c(Pd/Pt)-TS(O) are given in the Supporting Information.
-
-
-
-
74
-
-
0344670984
-
-
note
-
Me 6(Ni).
-
-
-
-
75
-
-
0344239520
-
-
note
-
PH3 6(Pt)).
-
-
-
-
77
-
-
0344670983
-
-
note
-
C(O)Me isomer is the most stable form for all three metals.
-
-
-
-
79
-
-
0344239521
-
-
note
-
Indeed, taking only the metal-ligand bond strengths into account suggests inserion into the M-Me bond would be slightly favored for M = Ni by 2.7 kcal/mol but that insertion into the M-OMe bonds would be favored by 1.0 and 5.5 kcal/mol for M = Pd and Pt, respectively.
-
-
-
-
80
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0003998388
-
-
Weast, R. C., Ed.; CRC Press Inc.: Boca Raton
-
CRC Handbook of Chemistry and Physics, Weast, R. C., Ed.; CRC Press Inc.: Boca Raton, 1981.
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(1981)
CRC Handbook of Chemistry and Physics
-
-
-
81
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0345101812
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note; Work in progress
-
Initial calculations indicate that CO migratory insertion with Ni - OPh bonds is significantly less favorale than the same reaction with Ni - OMe bonds. Neave, G. W. Work in progress.
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Neave, G.W.1
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