The synthesis and characterization of Re3(μ-H) 3(CO)9 - N(PMe3)n(μ3- η2:η2:η2-C60) (n = 2, 3) complexes

Hongkyu Kang; Bo Keun Park; Md Arzu Miah; Hyunjoon Song; David G. Churchill; Sangwoo Park; Moon Gun Choi; Joon T. Park

doi:10.1016/j.jorganchem.2005.07.052

The synthesis and characterization of Re₃(μ-H) ₃(CO)_{9 - N}(PMe₃)_n(μ₃- η²:η²:η²-C₆₀) (n = 2, 3) complexes

Hongkyu Kang, Bo Keun Park, Md Arzu Miah, Hyunjoon Song, David G. Churchill, Sangwoo Park, Moon Gun Choi, Joon T. Park

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

Abstract

Treatment of Re₃(μ-H)₃(CO) ₉(μ₃-η²:η²: η²-C₆₀) (1) with 2.2 equiv. of Me₃NO in the presence of excess PMe₃ in chlorobenzene (CB) gave the bisphosphine-substituted complex 1,2-Re₃(μ-H)₃(CO) ₇(PMe₃)₂(μ₃-η²: η²:η²-C₆₀) as two diastereomers, 2a (major, 38%) and 2b (minor, 11%). The corresponding reaction of 1 with 3.3 equiv. of Me₃NO, produced the trisphosphine-substituted isomeric product 1,2,3-Re₃(μ-H)₃(CO)₆(PMe ₃)₃(μ₃-η²:η²: η²-C₆₀) as two diastereomers, 3a (major, 37%) and 3b (minor, 15%). Complexes 2a-3b have been characterized by spectroscopic methods and elemental analyses. Single crystal X-ray diffraction studies were carried out for 2a and 3b. The hydrides were confirmed by ¹H NMR spectroscopic method and directly located only for 3a by X-ray diffraction. The molecular structure of 2a confirms a face-capping μ₃- η²:η²:η²-C₆₀ ligand with one axial and one equatorial PMe₃ ligand on adjacent rhenium atoms, whereas that for 3b exhibits pseudo-Cs symmetry with an additional equatorial PMe₃ on the third rhenium atom. Molecular structures for 2b and 3a are proposed by axial PMe₃ ligand placement and subsequent equatorial PMe₃ placement, based on earlier observations of facile ligand site-exchange in closely related systems and were verified by ¹H NMR spectroscopic method.

Original language	English
Pages (from-to)	4704-4711
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	690
Issue number	21-22
DOIs	https://doi.org/10.1016/j.jorganchem.2005.07.052
Publication status	Published - 2005 Nov 1

Bibliographical note

Funding Information:
This work was supported by the National Research Laboratory (NRL) Program of the Ministry of Science and Technology of Korea (MOST).

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.jorganchem.2005.07.052

Cite this

@article{4f77b3cd1098471e8db4073cffd7277f,

title = "The synthesis and characterization of Re3(μ-H) 3(CO)9 - N(PMe3)n(μ3- η2:η2:η2-C60) (n = 2, 3) complexes",

abstract = "Treatment of Re3(μ-H)3(CO) 9(μ3-η2:η2: η2-C60) (1) with 2.2 equiv. of Me3NO in the presence of excess PMe3 in chlorobenzene (CB) gave the bisphosphine-substituted complex 1,2-Re3(μ-H)3(CO) 7(PMe3)2(μ3-η2: η2:η2-C60) as two diastereomers, 2a (major, 38%) and 2b (minor, 11%). The corresponding reaction of 1 with 3.3 equiv. of Me3NO, produced the trisphosphine-substituted isomeric product 1,2,3-Re3(μ-H)3(CO)6(PMe 3)3(μ3-η2:η2: η2-C60) as two diastereomers, 3a (major, 37%) and 3b (minor, 15%). Complexes 2a-3b have been characterized by spectroscopic methods and elemental analyses. Single crystal X-ray diffraction studies were carried out for 2a and 3b. The hydrides were confirmed by 1H NMR spectroscopic method and directly located only for 3a by X-ray diffraction. The molecular structure of 2a confirms a face-capping μ3- η2:η2:η2-C60 ligand with one axial and one equatorial PMe3 ligand on adjacent rhenium atoms, whereas that for 3b exhibits pseudo-Cs symmetry with an additional equatorial PMe3 on the third rhenium atom. Molecular structures for 2b and 3a are proposed by axial PMe3 ligand placement and subsequent equatorial PMe3 placement, based on earlier observations of facile ligand site-exchange in closely related systems and were verified by 1H NMR spectroscopic method.",

author = "Hongkyu Kang and Park, {Bo Keun} and Miah, {Md Arzu} and Hyunjoon Song and Churchill, {David G.} and Sangwoo Park and Choi, {Moon Gun} and Park, {Joon T.}",

note = "Funding Information: This work was supported by the National Research Laboratory (NRL) Program of the Ministry of Science and Technology of Korea (MOST).",

year = "2005",

month = nov,

day = "1",

doi = "10.1016/j.jorganchem.2005.07.052",

language = "English",

volume = "690",

pages = "4704--4711",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "21-22",

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TY - JOUR

T1 - The synthesis and characterization of Re3(μ-H) 3(CO)9 - N(PMe3)n(μ3- η2:η2:η2-C60) (n = 2, 3) complexes

AU - Kang, Hongkyu

AU - Park, Bo Keun

AU - Miah, Md Arzu

AU - Song, Hyunjoon

AU - Churchill, David G.

AU - Park, Sangwoo

AU - Choi, Moon Gun

AU - Park, Joon T.

N1 - Funding Information: This work was supported by the National Research Laboratory (NRL) Program of the Ministry of Science and Technology of Korea (MOST).

PY - 2005/11/1

Y1 - 2005/11/1

N2 - Treatment of Re3(μ-H)3(CO) 9(μ3-η2:η2: η2-C60) (1) with 2.2 equiv. of Me3NO in the presence of excess PMe3 in chlorobenzene (CB) gave the bisphosphine-substituted complex 1,2-Re3(μ-H)3(CO) 7(PMe3)2(μ3-η2: η2:η2-C60) as two diastereomers, 2a (major, 38%) and 2b (minor, 11%). The corresponding reaction of 1 with 3.3 equiv. of Me3NO, produced the trisphosphine-substituted isomeric product 1,2,3-Re3(μ-H)3(CO)6(PMe 3)3(μ3-η2:η2: η2-C60) as two diastereomers, 3a (major, 37%) and 3b (minor, 15%). Complexes 2a-3b have been characterized by spectroscopic methods and elemental analyses. Single crystal X-ray diffraction studies were carried out for 2a and 3b. The hydrides were confirmed by 1H NMR spectroscopic method and directly located only for 3a by X-ray diffraction. The molecular structure of 2a confirms a face-capping μ3- η2:η2:η2-C60 ligand with one axial and one equatorial PMe3 ligand on adjacent rhenium atoms, whereas that for 3b exhibits pseudo-Cs symmetry with an additional equatorial PMe3 on the third rhenium atom. Molecular structures for 2b and 3a are proposed by axial PMe3 ligand placement and subsequent equatorial PMe3 placement, based on earlier observations of facile ligand site-exchange in closely related systems and were verified by 1H NMR spectroscopic method.

AB - Treatment of Re3(μ-H)3(CO) 9(μ3-η2:η2: η2-C60) (1) with 2.2 equiv. of Me3NO in the presence of excess PMe3 in chlorobenzene (CB) gave the bisphosphine-substituted complex 1,2-Re3(μ-H)3(CO) 7(PMe3)2(μ3-η2: η2:η2-C60) as two diastereomers, 2a (major, 38%) and 2b (minor, 11%). The corresponding reaction of 1 with 3.3 equiv. of Me3NO, produced the trisphosphine-substituted isomeric product 1,2,3-Re3(μ-H)3(CO)6(PMe 3)3(μ3-η2:η2: η2-C60) as two diastereomers, 3a (major, 37%) and 3b (minor, 15%). Complexes 2a-3b have been characterized by spectroscopic methods and elemental analyses. Single crystal X-ray diffraction studies were carried out for 2a and 3b. The hydrides were confirmed by 1H NMR spectroscopic method and directly located only for 3a by X-ray diffraction. The molecular structure of 2a confirms a face-capping μ3- η2:η2:η2-C60 ligand with one axial and one equatorial PMe3 ligand on adjacent rhenium atoms, whereas that for 3b exhibits pseudo-Cs symmetry with an additional equatorial PMe3 on the third rhenium atom. Molecular structures for 2b and 3a are proposed by axial PMe3 ligand placement and subsequent equatorial PMe3 placement, based on earlier observations of facile ligand site-exchange in closely related systems and were verified by 1H NMR spectroscopic method.

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