Enhancement in electronic communication upon replacement of Mo-O by Mo-S bonds in tetranuclear clusters of the type [Mo2]2(μ-E- E)2 (E = O or S)

Inorganic Chemistry

Volumn 46, Issue 22, 2007, Pages 9294-9302

  Cotton, F Albert ^a   Li, Zhong ^a   Liu, Chun Y ^a,b   Murillo, Carlos A ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

^b TONGJI UNIVERSITY   (China)

Author keywords

[No Author keywords available]

Indexed keywords

MOLYBDENUM; OXIDE; SULFUR;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; ELECTROCHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ULTRAVIOLET SPECTROPHOTOMETRY; X RAY CRYSTALLOGRAPHY;

CRYSTALLOGRAPHY, X-RAY; ELECTROCHEMISTRY; MAGNETIC RESONANCE SPECTROSCOPY; MODELS, MOLECULAR; MOLYBDENUM; OXIDES; SPECTROPHOTOMETRY, ULTRAVIOLET; SULFUR;

EID: 35848963211     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic701303k     Document Type: Article

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56. 2] unit.
57. A second crystallographic form of 3 was also observed. This form also had a structure of type A, but it had significant crystallographic disorder in the linker. Crystallographic data: space group P1, a = 10.443(4) Å b = 14.887(6) ̊ c = 23.587(10) Å, α = 87.848(7)°, β = 84.995(7)°, γ= 87.777(7)°, V = 3648(3) Å, Z = 2. It should be noted that so far there is no direct evidence for isomers of type B.
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60. Because of the active H atom in each of the hydroxyl bridging groups in 1, the electrochemical processes are irreversible.
61. 1/2 value is the same (450 mV) and similar to that in 2. Presumably, this is related to the two crystal forms mentioned in ref 30.
62. Note that there is a strong structural resemblance between 2 and 4 with the alkoxide analogues (see ref 15). For these alkoxides, the singly and doubly oxidized species were isolated and the oxidations were shown to be metal-based processes.
63. 2 nonbonding distance is reduced to 3.61 Å. See ref 14.
64. The reader should be cautioned that, because the oxidized species for 4 were not isolated, the second oxidation may have some ligand contribution and may not be entirely metal-based.
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66. It should be noted that the donation of electrons in the δ orbitals is unique to compounds with quadruply bonded units.
67. xy for S atoms (Schemes 4 and 5). In both cases, the corresponding contributions from S are greater than those from O for the HOMO - 1 and LUMO (see the Supporting Information).