Origin of the Enhancement of the Second Hyperpolarizabilities in Open-Shell Singlet Transition-Metal Systems with Metal–Metal Multiple Bonds

2011 ◽  
Vol 2 (16) ◽  
pp. 2063-2066 ◽  
Author(s):  
Hitoshi Fukui ◽  
Masayoshi Nakano ◽  
Yasuteru Shigeta ◽  
Benoît Champagne
Keyword(s):  
Transition Metal ◽  
Open Shell ◽  
Multiple Bonds ◽  
Metal Metal ◽  
Singlet Transition

Characterizations of Novel Binuclear Transition Metal Polynitrogen Compounds: M2(N5)4 (M=Co, Rh and Ir)

2014 ◽  
Vol 924 ◽  
pp. 233-252 ◽  
Author(s):  
Li Hong Tang ◽  
Hui Bin Guo ◽  
Qian Shu Li ◽  
Jin Hui Peng ◽  
Jun Jie Gu ◽  
...  
Keyword(s):  
Transition Metal ◽  
Nbo Analysis ◽  
High Order ◽  
Multiple Bonds ◽  
Dissociation Energies ◽  
Nucleus Independent Chemical Shift ◽  
Metal Atoms ◽  
Metal Metal ◽  
Natural Bonding Orbital ◽  
Polynitrogen Compounds

Theoretical studies on a series of binuclear transition metal pentazolides M2(N5)4(M=Co, Rh and Ir) predict Paddlewheel-type structures with very short metal-metal distances suggesting high-order metal-metal multiple bonds. Natural Bonding Orbital (NBO) analysis have indicated that the bonding between the metal atom and the five-membered ring is predominantly ionic for each M2(N5)4species, and a high-order metal-metal multiple bonding exists between the two metal atoms, in addition, the presence of the delocalized π orbital plays an important role in the stabilization of this metal-polynitrogen species. Nucleus independent chemical shift (NICS) values confirm that the planar N5exhibits aromaticity in these M2(N5)4species. The values of NICS(0.0), NICS(0.5) and NICS(1.0) for Co2(N5)4are larger than those of the other two M2(N5)4species (M=Rh and Ir), with the order of Co2(N5)4>Rh2(N5)4>Ir2(N5)4. The dissociation energies into Mononuclear Fragments for M2(N5)4(M=Co, Rh and Ir) are predicted to be 82.9 (85.7), 139.9 (113.2), and 155.1 (149.7) kcal/mol, respectively. However, the dissociation energies for the loss of one pentazolato group from the M2(N5)4analysis have indicated that the Co2(N5)4is relatively higher at ~40 kcal/mol. Thermochemistry suggests Co2(N5)4to be a viable species.

Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes

2014 ◽  
Vol 608 ◽  
pp. 68-73 ◽  
Author(s):  
Taishi Yamada ◽  
Shota Takamuku ◽  
Hiroshi Matsui ◽  
Benoît Champagne ◽  
Masayoshi Nakano
Keyword(s):  
Transition Metal ◽  
Open Shell ◽  
Axial Ligand ◽  
Dinuclear Complexes ◽  
Ligand Effects ◽  
Singlet Transition

ChemInform Abstract: TRANSITION METAL METHYLENE COMPLEXES. XXVIII. CARBENE ADDITION TO METAL-METAL L MULTIPLE BONDS. SYNTHESIS AND MOLECULAR STRUCTURES OF NOVEL μ-METHYLENE RHODIUM COMPLEXES

1982 ◽  
Vol 13 (23) ◽  
Author(s):  
W. A. HERRMANN ◽  
C. BAUER ◽  
G. KRIECHBAUM ◽  
H. KUNKELY ◽  
M. L. ZIEGLER ◽  
...  
Keyword(s):  
Transition Metal ◽  
Molecular Structures ◽  
Rhodium Complexes ◽  
Multiple Bonds ◽  
Metal Metal

Enhancement of the Third-Order Nonlinear Optical Properties in Open-Shell Singlet Transition-Metal Dinuclear Systems: Effects of the Group, of the Period, and of the Charge of the Metal Atom

2012 ◽  
Vol 116 (22) ◽  
pp. 5501-5509 ◽  
Author(s):  
Hitoshi Fukui ◽  
Yudai Inoue ◽  
Taishi Yamada ◽  
Soichi Ito ◽  
Yasuteru Shigeta ◽  
...  
Keyword(s):  
Optical Properties ◽  
Transition Metal ◽  
Metal Atom ◽  
Nonlinear Optical ◽  
Open Shell ◽  
Nonlinear Optical Properties ◽  
Third Order ◽  
The Third ◽  
Singlet Transition

Metal-metal multiple bonds. 15. Syntheses and structures of the 17-electron radical TpMo(CO)3 and the triply bonded dimer Tp2Mo2(CO)4(Mo.tplbond.Mo) (Tp = hydridotris(pyrazolyl)borate)

1983 ◽  
Vol 2 (7) ◽  
pp. 936-938 ◽  
Author(s):  
Komb Bei Shiu ◽  
M. David Curtis ◽  
John C. Huffman
Keyword(s):  
Multiple Bonds ◽  
Metal Metal
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