Metal Germylyne Complexes [M⋮Ge−R] and Metallogermylenes [M−Ge−R]: DFT Analysis of the Systems [(Cp)(CO)nM⋮GeMe] (M = Cr, Mo, W, Fe2+, n = 2; M = Fe, n = 1) and [(Cp)(CO)nM−GeMe] (M = Cr, Mo, W, n = 3; M = Fe, n = 2)
作者： Krishna K. Pandey , Matthias Lein , Gernot Frenking
DOI: 10.1021/JA020974M
关键词: Electrostatic attraction 、 Quantum chemical 、 Covalent bond 、 Iron complex 、 Bond length 、 Molecule 、 Crystallography 、 Stereochemistry 、 Electronic structure 、 Chemistry 、 Metal
摘要: Quantum chemical calculations at the gradient corrected DFT level using exchange correlation functionals BP86 and B3LYP of geometries title compounds are reported. The theoretically predicted bond lengths angles model in excellent agreement with experiment. nature metal−ligand interactions is quantitatively analyzed an energy decomposition method. analysis electronic structure neutral metal germylyne complexes Ia−Id metallogermylenes IIa−IId shows that former have about same degree electrostatic covalent bonding, while relative strength contributions latter molecules lower (41−42%) than attraction (58−59%). a‘ ‘(π) bonding contribution group-6 Ia−Ic rather high (42% orbital interactions). In iron complex Id, it even higher (53.8%) σ bonding. π to beco...
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sci-hub.se 参考文章(62)
J.G. Snijders, P. Vernooijs, E.J. Baerends, Roothaan-Hartree-Fock-Slater atomic wave functions Atomic Data and Nuclear Data Tables. ,vol. 26, pp. 483- 509 ,(1981) , 10.1016/0092-640X(81)90004-8
Jamal Uddin, Gernot Frenking, Energy Analysis of Metal-Ligand Bonding in Transition Metal Complexes with Terminal Group-13 Diyl Ligands (CO)4Fe-ER, Fe(EMe)5 and Ni(EMe)4 (E = B−Tl; R = Cp, N(SiH3)2, Ph, Me) Reveals Significant π Bonding in Homoleptical Molecules‡ Journal of the American Chemical Society. ,vol. 123, pp. 1683- 1693 ,(2001) , 10.1021/JA002845G
P. Jeffrey Hay, Willard R. Wadt, Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals Journal of Chemical Physics. ,vol. 82, pp. 299- 310 ,(1985) , 10.1063/1.448975
J-L Heully, Ingvar Lindgren, Eva Lindroth, Stig Lundqvist, A-M Martensson-Pendrill, None, Diagonalisation of the Dirac Hamiltonian as a basis for a relativistic many-body procedure Journal of Physics B. ,vol. 19, pp. 2799- 2815 ,(1986) , 10.1088/0022-3700/19/18/011
Keiji Morokuma, Molecular Orbital Studies of Hydrogen Bonds. III. C=O···H–O Hydrogen Bond in H2CO···H2O and H2CO···2H2O The Journal of Chemical Physics. ,vol. 55, pp. 1236- 1244 ,(1971) , 10.1063/1.1676210
Peter Jutzi, Holger Schmidt, Beate Neumann, Hans-Georg Stammler, Bis(2,4,6-tri-tert-butylphenyl)germylene Reinvestigated: Crystal Structure, Lewis Acid Catalyzed C−H Insertion, and Oxidation to an Unstable Germanone Organometallics. ,vol. 15, pp. 741- 746 ,(1996) , 10.1021/OM950558T
R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions Journal of Chemical Physics. ,vol. 72, pp. 650- 654 ,(1980) , 10.1063/1.438955
Michael F. Lappert, Robert S. Rowe, The role of group 14 element carbene analogues in transition metal chemistry Coordination Chemistry Reviews. ,vol. 100, pp. 267- 292 ,(1990) , 10.1016/0010-8545(90)85012-H
Francis Carre, Ernesto Colomer, Robert J. P. Corriu, Andre Vioux, Transition-metal complexes corresponding to the insertion into a Group 4A element-carbon bond. 3. Reactivity of complexes with unsaturated carbon-carbon bonds. Crystal structure of (.eta.5-cyclopentadienyl)(triphenylgermyl)(.eta.3-hexenyl)nitrosylmolybdenum Organometallics. ,vol. 3, pp. 970- 977 ,(1984) , 10.1021/OM00085A003
A. D. McLean, G. S. Chandler, Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 Journal of Chemical Physics. ,vol. 72, pp. 5639- 5648 ,(1980) , 10.1063/1.438980