Metal-metal multiple bonds. 10. Electrophilic additions of halogens and hydrogen halides to the molybdenum-molybdenum triple bond in dicyclopentadienyldimolybdenum tetracarbonyl

1983 ◽  
Vol 105 (9) ◽  
pp. 2686-2694 ◽  
Author(s):  
M. David Curtis ◽  
Nicephoros A. Fotinos ◽  
Kyoung R. Han ◽  
William M. Butler
Keyword(s):  
Triple Bond ◽  
Multiple Bonds ◽  
Hydrogen Halides ◽  
Metal Metal ◽  
Electrophilic Additions

Metal-metal multiple bonds. 18. Addition reactions of diazoalkanes with the molybdenum-molybdenum triple bond in R2Mo2(CO)4 (R = C5H5, C5H4Me, C5Me5)

1986 ◽  
Vol 5 (11) ◽  
pp. 2283-2294 ◽  
Author(s):  
M. David. Curtis ◽  
L. Messerle ◽  
John J. D'Errico ◽  
William M. Butler ◽  
Michael S. Hay
Keyword(s):  
Triple Bond ◽  
Addition Reactions ◽  
Multiple Bonds ◽  
Metal Metal

scholarly journals Identification of a uranium–rhodium triple bond in a heterometallic cluster

2019 ◽  
Vol 116 (36) ◽  
pp. 17654-17658 ◽  
Author(s):  
Genfeng Feng ◽  
Mingxing Zhang ◽  
Penglong Wang ◽  
Shuao Wang ◽  
Laurent Maron ◽  
...  
Keyword(s):  
Triple Bond ◽  
Covalent Bond ◽  
Small Molecule Activation ◽  
X Ray Diffraction ◽  
Multiple Bonds ◽  
Uranium Metal ◽  
Heterometallic Cluster ◽  
Metal Metal ◽  
Metal Bonds

The chemistry of d-block metal–metal multiple bonds has been extensively investigated in the past 5 decades. However, the synthesis and characterization of species with f-block metal–metal multiple bonds are significantly more challenging and such species remain extremely rare. Here, we report the identification of a uranium–rhodium triple bond in a heterometallic cluster, which was synthesized under routine conditions. The uranium–rhodium triple-bond length of 2.31 Å in this cluster is only 3% longer than the sum of the covalent triple-bond radii of uranium and rhodium (2.24 Å). Computational studies reveal that the nature of this uranium–rhodium triple bond is 1 covalent bond with 2 rhodium-to-uranium dative bonds. This heterometallic cluster represents a species with f-block metal–metal triple bond structurally authenticated by X-ray diffraction. These studies not only demonstrate the authenticity of the uranium–metal triple bond, but also provide a possibility for the synthesis of other f-block metal–metal multiple bonds. We expect that this work may further our understanding of the bonding between uranium and transition metals, which may help to design new d-f heterometallic catalysts with uranium–metal bonds for small-molecule activation and to promote the utilization of abundant depleted uranium resources.

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.

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