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Volumn 49, Issue 39, 2010, Pages 7106-7110

Carbodiylides C(ECp*)2 (E = B-Tl): Another class of theoretically predicted divalent carbon(0) compounds

Author keywords

Carbodiylides; Carbones; Density functional calculations; Divalent carbon; Donor acceptor complexes

Indexed keywords

CARBODIYLIDES; CARBONES; DENSITY FUNCTIONAL CALCULATIONS; DIVALENT CARBON; DONOR-ACCEPTOR COMPLEX;

EID: 77956898894     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201002773     Document Type: Article
Times cited : (23)

References (75)
  • 20
    • 67849119716 scopus 로고    scopus 로고
    • Chemical bonding: Rethinking carbon
    • "Chemical Bonding: Rethinking Carbon": C. A. Dyker, G. Bertrand, Nat. Chem. 2009, 1, 265.
    • (2009) Nat. Chem. , vol.1 , pp. 265
    • Dyker, C.A.1    Bertrand, G.2
  • 47
    • 77956901634 scopus 로고    scopus 로고
    • 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
    • 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.
  • 49
    • 77956907424 scopus 로고    scopus 로고
    • 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.
  • 50
    • 77956928996 scopus 로고    scopus 로고
    • 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.
  • 51
    • 77956893866 scopus 로고    scopus 로고
    • 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
    • 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.
  • 60
    • 0038626673 scopus 로고    scopus 로고
    • Rev. D. 01, M. J. Frisch etal. , Gaussian, Inc. , Wallingford CT, for the full reference, see the Supporting Information
    • Gaussian 03, Rev. D. 01, M. J. Frisch etal. , Gaussian, Inc. , Wallingford CT, 2004; for the full reference, see the Supporting Information.
    • (2004) Gaussian 03


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.