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Geometry optimizations without symmetry constraints were carried out using the Gaussian03 optimizer together with TurboMole6. 0. 2 energies and gradients at the BP86/def2- SVP[21a] level of theory (called BP86/SVP). Small-core ECPs[21b] were used for the elements In and Tl. Stationary points were characterized as minima by calculating the Hessian matrix analytically at this level. Thermodynamic corrections were taken from these calculations. The standard state for all thermody- namic data was 298. 15 K and 1 atm. Single-point energies were calculated for some molecules with the MP2 method using the def2-TZVPP (called TZVPP) basis set. The resolution-of-identity method has been used for the MP2 and BP86 calculations. The atomic partial charges were calculated with the NBO method at BP86/TZVPP without RI approximation on the BP86/SVP geometries
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Geometry optimizations without symmetry constraints were carried out using the Gaussian03 optimizer together with TurboMole6. 0. 2 energies and gradients at the BP86/def2- SVP[21a] level of theory (called BP86/SVP). Small-core ECPs[21b] were used for the elements In and Tl. Stationary points were characterized as minima by calculating the Hessian matrix analytically at this level. Thermodynamic corrections were taken from these calculations. The standard state for all thermody- namic data was 298. 15 K and 1 atm. Single-point energies were calculated for some molecules with the MP2 method using the def2-TZVPP (called TZVPP) basis set. The resolution-of-identity method has been used for the MP2 and BP86 calculations. The atomic partial charges were calculated with the NBO method at BP86/TZVPP without RI approximation on the BP86/SVP geometries.
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49
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77956907424
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The equilibrium structures of the heavier parent systems C(EH)2, where E = Al-Tl, also have strongly bent geometries at the BP86/SVP level: the bending angle E-C-E is between 100. 5° (E = Al) and 109. 0° (E = Tl), which correlates with the strongly bent structures of the systems C(ECp*)2. The linear structures of C(EH)2 and C(ECp*)2 (E = Al-Tl) are not minima on the singlet potential-energy surface
-
The equilibrium structures of the heavier parent systems C(EH)2, where E = Al-Tl, also have strongly bent geometries at the BP86/SVP level: the bending angle E-C-E is between 100. 5° (E = Al) and 109. 0° (E = Tl), which correlates with the strongly bent structures of the systems C(ECp*)2. The linear structures of C(EH)2 and C(ECp*)2 (E = Al-Tl) are not minima on the singlet potential-energy surface.
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50
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77956928996
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C(BH)2 has a higher- lying local energy minimum at BP86/SVP, which is strongly bent (bending angle 93. 4°), that is 3. 4 kcalmor-1 less stable than the linear form. The bent form of C(BH)2 has a very shallow energy minimum on the PES, which requires less than 1 kcalmor-1 activation energy to yield the linear energy minimum form. There are no local energy minima with linear geometry for C(EH)22 (E = Al-Tl). Preliminary calculations suggest that the preference for the bent structures of C(EH)2 correlates with the singlet-triplet gap of EH
-
C(BH)2 has a higher- lying local energy minimum at BP86/SVP, which is strongly bent (bending angle 93. 4°), that is 3. 4 kcalmor-1 less stable than the linear form. The bent form of C(BH)2 has a very shallow energy minimum on the PES, which requires less than 1 kcalmor-1 activation energy to yield the linear energy minimum form. There are no local energy minima with linear geometry for C(EH)22 (E = Al-Tl). Preliminary calculations suggest that the preference for the bent structures of C(EH)2 correlates with the singlet-triplet gap of EH.
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2 are slightly different for the two ligands Ecp*, but the differences are not very large. The full set of bond lengths and angles is given in the Supporting Information, Table S1
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2 are slightly different for the two ligands Ecp*, but the differences are not very large. The full set of bond lengths and angles is given in the Supporting Information, Table S1.
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