The nature of the bonding in transition-metal compounds.

Quantum-chemical calculations with DFT (BP86) and ab initio methods [MP2, SCS-MP2, CCSD(T)] have been carried out for the molecules C(PH(3))(2) (1), C(PMe(3))(2) (2), C(PPh(3))(2) (3), C(PPh(3))(CO) (4), C(CO)(2) (5), C(NHC(H))(2) (6), C(NHC(Me))(2) (7) (Me(2)N)(2)C=C=C(NMe(2))(2) (8), and NHC (9), where NHC=N-heterocyclic carbene and NHC(Me)=N-methyl-substituted NHC. The electronic structure in 1-9 was analyzed with charge- and energy-partitioning methods. The results show that the bonding situations in L(2)C compounds 1-8 can be interpreted in terms of donor-acceptor interactions between closed-shell ligands L and a carbon atom which has two lone-pair orbitals L-->C C((1)D) donor-acceptor bonds are roughly twice as strong as the respective L-->BH(3) bond.

Divalent Carbon(0) Chemistry, Part 1: Parent Compounds

2.2.1. Diaminoand Aminohydrazinocarbenes 3338 2.2.2. Aminothioand Aminooxycarbenes 3340 2.3. Phosphinoaryland Phosphinoalkylcarbenes 3341 2.4. Aminoaryland Aminoalkylcarbenes 3344 2.5. Aminophosphonio and Aminosilylcarbenes 3346 2.6. Aminophosphinocarbenes 3347 3. Reactivity 3348 3.1. Typical Carbene Behavior 3348 3.1.1. Coupling Reactions 3348 3.1.2. Cycloaddition Reactions 3352 3.1.3. Insertion Reactions 3355 3.1.4. Migration Reactions 3358 3.2. Basic/Nucleophilic Behavior 3359 3.2.1. Protonation of Carbenes 3359 3.2.2. Reactions with Group 14 Electrophiles 3360 3.2.3. Reactions with Group 13 Lewis Acids 3360 3.2.4. Reactions with Group 15 Electrophiles 3361 3.3. Electrophilic Behavior 3362 3.3.1. Reaction with 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN) 3362

Stable Noncyclic Singlet Carbenes

Group 13 metal (Al, Ga, In, Tl) complexes supported by heteroatom-bonded carbene ligands

The very strong solid Lewis acids aluminium chlorofluoride (ACF) and bromofluoride (ABF)—Synthesis, structure, and Lewis acidity

Quantum chemical calculations at the MP2 level using large valence basis sets up to TZ+2P quality have been carried out in order to predict the geometries and bond energies of the title compounds. The nature of the donor–acceptor bond has also been investigated. The calculations show clearly that diaminocarbenes are much stronger Lewis bases than amines. The complexation energies of C(NH2)2 have been calculated to be 14–27 kcal/mol higher than those of NH3. The most strongly bonded complex is Cl3Al–C(NH2)2, which has a theoretically predicted Al–C bond energy Do = 59.1 kcal/mol. In all the complexes, the strength of the Lewis bases is C(NH2)2 > NH3 > CO, but the ordering of Lewis acid strength of EX3 depends on the coordinated Lewis base. TiF4 and TiCl4 have similar Lewis acidities as BF3, but the titanium tetrahalides may bind one or two donor molecules with almost the same bond strength. The investigated donor–acceptor bonds have a high degree of ionic character. The largest covalent contributions are found for the diaminocarbene complexes. The covalent character of the X3E–CO bond increases on going from E = boron to the heavier Group 13 elements, while the opposite order is found for the X3E–NH3 and X3E–C(NH2)2 bonds.

The Lewis Basicity of Diaminocarbene – A Theoretical Study of Donor–Acceptor Complexes of C(NH2)2, NH3 and CO with the Lewis Acids EF3, ECl3 (E = B, Al, Ga, In), TiF4 and TiCl4

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The Lewis Basicity of Diaminocarbene – A Theoretical Study of Donor–Acceptor Complexes of C(NH2)2, NH3 and CO with the Lewis Acids EF3, ECl3 (E = B, Al, Ga, In), TiF4 and TiCl4