Optimizing the Nonlinear Optical Performance of an A-N-M-Q (A: Alkali Metal; N: d10 Metal; M: Main Group Metal; Q: Chalcogen) System

Abstract The M–Ccarbene bond in metal (M) complexes involving the imidazol-2-ylidene (Im) ligand has largely been described using the σ-donor only model with donation of σ electrons from the sp-hybridized orbital of the carbene carbon into vacant orbitals on the metal centre. Analyses of the M–Ccarbene bond in a series of group IA, IIA and IIIA main group metal complexes show that the M-Im interactions are mostly electrostatic with the M–Ccarbene bond distances greater than the sum of the respective covalent radii. Estimation of the binding energies of a series of metal hydride/fluoride/chloride imidazol-2-ylidene complexes revealed that the stability of the M–Ccarbene bond in these complexes is not always commensurate with the σ-only electrostatic model. Further natural bond orbital (NBO) analyses at the DFT/B3LYP level of theory revealed substantial covalency in the M–Ccarbene bond with minor delocalization of electron density from the lone pair electrons on the halide ligands into antibonding molecular orbitals on the Im ligand. Calculation of the thermodynamic stability of the M–Ccarbene bond showed that these interactions are mostly endothermic in the gas phase with reduced entropies giving an overall ΔG > 0.

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Studies on main group metal-transition metal bonded compounds. 3. Synthesis and structure of (.eta.-cyclopentadienyl)tricarbonylmolybdenum zinc monobromide.2THF and tetrabutylammonium (.eta.-cyclopentadienyl)tricarbonylmolybdenum

Inorganic Chemistry ◽

10.1021/ic50170a040 ◽

1977 ◽

Vol 16 (4) ◽

pp. 920-924 ◽

Cited By ~ 32

Author(s):

David E. Crotty ◽

Eugene R. Corey ◽

Thomas J. Anderson ◽

Milton D. Glick ◽

John P. Oliver

Keyword(s):

Transition Metal ◽

Main Group ◽

Group Metal ◽

Main Group Metal

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Studies on main group metal-transition-metal bonded compounds 7. A 199Hg NMR study of home group of some group VI trasition-metal mercury compounds

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(00)81860-4 ◽

1979 ◽

Vol 172 (1) ◽

pp. 99-107 ◽

Cited By ~ 20

Author(s):

M.J. Albright ◽

J.P. Oliver

Keyword(s):

Transition Metal ◽

Main Group ◽

Group Vi ◽

Mercury Compounds ◽

Group Metal ◽

Home Group ◽

Nmr Study ◽

Main Group Metal

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ProPhenol Derived Ligands to Simultaneously Coordinate a Main Group‐Metal and a Transition Metal: Application to a Zn‐Cu Catalyzed Reaction

Chemistry - A European Journal ◽

10.1002/chem.202104268 ◽

2021 ◽

Author(s):

Barry M. Trost ◽

Guoting Zhang ◽

Minghao Xu ◽

Xiaotian Qi

Keyword(s):

Transition Metal ◽

Main Group ◽

Group Metal ◽

Main Group Metal

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Main-group metal complexes of α-diimine ligands: structure, bonding and reactivity

Dalton Transactions ◽

10.1039/d1dt02120f ◽

2021 ◽

Author(s):

Rong Zhang ◽

Yanchao Wang ◽

Yanxia Zhao ◽

Carl Redshaw ◽

Igor L. Fedushkin ◽

...

Keyword(s):

Metal Complexes ◽

Small Molecule ◽

Main Group ◽

Group Metal ◽

Diimine Ligands ◽

Main Group Metal ◽

Metal Metal ◽

Low Valent

The use of dad (and bian) ligands in the stabilization of main-group complexes, in particular metal–metal-bonded compounds, as well as the small molecule reactivity of these (low-valent) metal complexes, is summarized.

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