Homologues of the easily ionized compound Mo2(hpp)4 containing smaller bicyclic guanidinates

F. Albert Cotton; Carlos A. Murillo; Xiaoping Wang; Chad C. Wilkinson

doi:10.1021/ic060449e

Homologues of the easily ionized compound Mo₂(hpp)₄ containing smaller bicyclic guanidinates

F. Albert Cotton, Carlos A. Murillo, Xiaoping Wang, Chad C. Wilkinson

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45 Scopus citations

Abstract

Two bicyclic guanidinate ligands consisting of 5,5-membered (tbo) and 5,6-membered (tbn) rings have been used for the preparation of dimolybdenum compounds, such as Mo₂(tbo)₄ and Mo₂(tbo) ₄CI, and species containing Mo₂(tbn)₄ ⁿ⁺ with n = 0-2. The compounds with quadruply bonded Mo ₂⁴⁺ species are strong reducing agents and have potentials of about -1 V (vs Ag/AgCl) for the Mo₂^5+/4+ process. The structure of the THF solvate of Mo₂(tbo)₄ shows the longest Mo-Mo bond distance, 2.1453(4) Å, for a quadruply bonded species, and this is due to a large divergent angle induced by the geometry of the ligand. This distance increases to 2.2305(8) Å upon oxidation by CH ₂Cl₂ to Mo₂(tbo)₄Cl. For the 5,6-membered-ring ligand tbn, even though the divergent angle is large compared to formamidinate ligands, it is not as large as that in tbo, and the Mo-Mo distance in Mo₂(tbn)₄, 2.082(1) Å, is in the normal range for paddlewheel Mo₂⁴⁺ compounds. This distance increases to 2.2233(8) Å upon oxidation by O₂ in CH ₂Cl₂, which forms Mo₂(tbn)₄Cl ₂·CH₂Cl₂.

Original language	English
Pages (from-to)	5493-5500
Number of pages	8
Journal	Inorganic Chemistry
Volume	45
Issue number	14
DOIs	https://doi.org/10.1021/ic060449e
State	Published - Jul 10 2006
Externally published	Yes

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@article{3a2d6bd7ee904bf48528200d453af91a,

title = "Homologues of the easily ionized compound Mo2(hpp)4 containing smaller bicyclic guanidinates",

abstract = "Two bicyclic guanidinate ligands consisting of 5,5-membered (tbo) and 5,6-membered (tbn) rings have been used for the preparation of dimolybdenum compounds, such as Mo2(tbo)4 and Mo2(tbo) 4CI, and species containing Mo2(tbn)4 n+ with n = 0-2. The compounds with quadruply bonded Mo 24+ species are strong reducing agents and have potentials of about -1 V (vs Ag/AgCl) for the Mo25+/4+ process. The structure of the THF solvate of Mo2(tbo)4 shows the longest Mo-Mo bond distance, 2.1453(4) {\AA}, for a quadruply bonded species, and this is due to a large divergent angle induced by the geometry of the ligand. This distance increases to 2.2305(8) {\AA} upon oxidation by CH 2Cl2 to Mo2(tbo)4Cl. For the 5,6-membered-ring ligand tbn, even though the divergent angle is large compared to formamidinate ligands, it is not as large as that in tbo, and the Mo-Mo distance in Mo2(tbn)4, 2.082(1) {\AA}, is in the normal range for paddlewheel Mo24+ compounds. This distance increases to 2.2233(8) {\AA} upon oxidation by O2 in CH 2Cl2, which forms Mo2(tbn)4Cl 2·CH2Cl2.",

author = "Cotton, {F. Albert} and Murillo, {Carlos A.} and Xiaoping Wang and Wilkinson, {Chad C.}",

year = "2006",

month = jul,

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doi = "10.1021/ic060449e",

language = "English",

volume = "45",

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journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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T1 - Homologues of the easily ionized compound Mo2(hpp)4 containing smaller bicyclic guanidinates

AU - Cotton, F. Albert

AU - Murillo, Carlos A.

AU - Wang, Xiaoping

AU - Wilkinson, Chad C.

PY - 2006/7/10

Y1 - 2006/7/10

N2 - Two bicyclic guanidinate ligands consisting of 5,5-membered (tbo) and 5,6-membered (tbn) rings have been used for the preparation of dimolybdenum compounds, such as Mo2(tbo)4 and Mo2(tbo) 4CI, and species containing Mo2(tbn)4 n+ with n = 0-2. The compounds with quadruply bonded Mo 24+ species are strong reducing agents and have potentials of about -1 V (vs Ag/AgCl) for the Mo25+/4+ process. The structure of the THF solvate of Mo2(tbo)4 shows the longest Mo-Mo bond distance, 2.1453(4) Å, for a quadruply bonded species, and this is due to a large divergent angle induced by the geometry of the ligand. This distance increases to 2.2305(8) Å upon oxidation by CH 2Cl2 to Mo2(tbo)4Cl. For the 5,6-membered-ring ligand tbn, even though the divergent angle is large compared to formamidinate ligands, it is not as large as that in tbo, and the Mo-Mo distance in Mo2(tbn)4, 2.082(1) Å, is in the normal range for paddlewheel Mo24+ compounds. This distance increases to 2.2233(8) Å upon oxidation by O2 in CH 2Cl2, which forms Mo2(tbn)4Cl 2·CH2Cl2.

AB - Two bicyclic guanidinate ligands consisting of 5,5-membered (tbo) and 5,6-membered (tbn) rings have been used for the preparation of dimolybdenum compounds, such as Mo2(tbo)4 and Mo2(tbo) 4CI, and species containing Mo2(tbn)4 n+ with n = 0-2. The compounds with quadruply bonded Mo 24+ species are strong reducing agents and have potentials of about -1 V (vs Ag/AgCl) for the Mo25+/4+ process. The structure of the THF solvate of Mo2(tbo)4 shows the longest Mo-Mo bond distance, 2.1453(4) Å, for a quadruply bonded species, and this is due to a large divergent angle induced by the geometry of the ligand. This distance increases to 2.2305(8) Å upon oxidation by CH 2Cl2 to Mo2(tbo)4Cl. For the 5,6-membered-ring ligand tbn, even though the divergent angle is large compared to formamidinate ligands, it is not as large as that in tbo, and the Mo-Mo distance in Mo2(tbn)4, 2.082(1) Å, is in the normal range for paddlewheel Mo24+ compounds. This distance increases to 2.2233(8) Å upon oxidation by O2 in CH 2Cl2, which forms Mo2(tbn)4Cl 2·CH2Cl2.

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JF - Inorganic Chemistry

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ER -

Homologues of the easily ionized compound Mo₂(hpp)₄ containing smaller bicyclic guanidinates

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