Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re6(μ3-Se) 8]2+ core-containing clusters

Xiaoyan Tu; Ethan Boroson; Huong Truong; Alvaro Muñoz-Castro; Ramiro Arratia-Pérez; Gary S. Nichol; Zhiping Zheng

doi:10.1021/ic902251z

Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re₆(μ₃-Se) ₈]²⁺ core-containing clusters

Xiaoyan Tu, Ethan Boroson, Huong Truong, Alvaro Muñoz-Castro, Ramiro Arratia-Pérez, Gary S. Nichol, Zhiping Zheng

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

15 Scopus citations

Abstract

The reactions of C₆H₅CH(CH₃)N₃ with nitrlle solvates of the [Re₆(μ₃-Se) ₈]²⁺ core-containing cluster, [Re₆(μ ₃-Se)₈(PEt₃)₅-(MeCN)] ²⁺(1) and cis-[Re₆(μ₃-Se) ₈(PEt₃)₄(MeCN)₂]²⁺ (2), afforded the corresponding cationlc imino complexes [Re₆(μ ₃3-Se)₈-(PEt₃)₅(PhN=CHCH ₃)²⁺ (3) and cis-[Re₆(μ₃-Se) ₈(PEt₃)₄(PhN= CHCH₃) ₂]²⁺ (4), respectively. Both compounds were spectroscopically and crystallographically characterized. A mechanism involving a 1,2-shift of one of the groups on the azido α-C atom of the cluster-azide intermediate conceited with the photoexpulsion of dinitrogen of the azido ligand is invoked to rationalize the formation of the imino complexes. Density functional theory calculations showed that a cluster-to-ligand transition was responsible for the absorption that promotes the photodecomposition of the cluster-azide complex.

Original language	English (US)
Pages (from-to)	380-382
Number of pages	3
Journal	Inorganic Chemistry
Volume	49
Issue number	2
DOIs	https://doi.org/10.1021/ic902251z
State	Published - Jan 18 2010
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic902251z

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@article{c5405a0e97f24c7bb10cf78654460801,

title = "Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re6(μ3-Se) 8]2+ core-containing clusters",

abstract = "The reactions of C6H5CH(CH3)N3 with nitrlle solvates of the [Re6(μ3-Se) 8]2+ core-containing cluster, [Re6(μ 3-Se)8(PEt3)5-(MeCN)] 2+(1) and cis-[Re6(μ3-Se) 8(PEt3)4(MeCN)2]2+ (2), afforded the corresponding cationlc imino complexes [Re6(μ 33-Se)8-(PEt3)5(PhN=CHCH 3)2+ (3) and cis-[Re6(μ3-Se) 8(PEt3)4(PhN= CHCH3) 2]2+ (4), respectively. Both compounds were spectroscopically and crystallographically characterized. A mechanism involving a 1,2-shift of one of the groups on the azido α-C atom of the cluster-azide intermediate conceited with the photoexpulsion of dinitrogen of the azido ligand is invoked to rationalize the formation of the imino complexes. Density functional theory calculations showed that a cluster-to-ligand transition was responsible for the absorption that promotes the photodecomposition of the cluster-azide complex.",

author = "Xiaoyan Tu and Ethan Boroson and Huong Truong and Alvaro Mu{\~n}oz-Castro and Ramiro Arratia-P{\'e}rez and Nichol, {Gary S.} and Zhiping Zheng",

year = "2010",

month = jan,

day = "18",

doi = "10.1021/ic902251z",

language = "English (US)",

volume = "49",

pages = "380--382",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Cluster-bound nitriles do not click with organic azides

T2 - Unexpected formation of imino complexes of the [Re6(μ3-Se) 8]2+ core-containing clusters

AU - Tu, Xiaoyan

AU - Boroson, Ethan

AU - Truong, Huong

AU - Muñoz-Castro, Alvaro

AU - Arratia-Pérez, Ramiro

AU - Nichol, Gary S.

AU - Zheng, Zhiping

PY - 2010/1/18

Y1 - 2010/1/18

N2 - The reactions of C6H5CH(CH3)N3 with nitrlle solvates of the [Re6(μ3-Se) 8]2+ core-containing cluster, [Re6(μ 3-Se)8(PEt3)5-(MeCN)] 2+(1) and cis-[Re6(μ3-Se) 8(PEt3)4(MeCN)2]2+ (2), afforded the corresponding cationlc imino complexes [Re6(μ 33-Se)8-(PEt3)5(PhN=CHCH 3)2+ (3) and cis-[Re6(μ3-Se) 8(PEt3)4(PhN= CHCH3) 2]2+ (4), respectively. Both compounds were spectroscopically and crystallographically characterized. A mechanism involving a 1,2-shift of one of the groups on the azido α-C atom of the cluster-azide intermediate conceited with the photoexpulsion of dinitrogen of the azido ligand is invoked to rationalize the formation of the imino complexes. Density functional theory calculations showed that a cluster-to-ligand transition was responsible for the absorption that promotes the photodecomposition of the cluster-azide complex.

AB - The reactions of C6H5CH(CH3)N3 with nitrlle solvates of the [Re6(μ3-Se) 8]2+ core-containing cluster, [Re6(μ 3-Se)8(PEt3)5-(MeCN)] 2+(1) and cis-[Re6(μ3-Se) 8(PEt3)4(MeCN)2]2+ (2), afforded the corresponding cationlc imino complexes [Re6(μ 33-Se)8-(PEt3)5(PhN=CHCH 3)2+ (3) and cis-[Re6(μ3-Se) 8(PEt3)4(PhN= CHCH3) 2]2+ (4), respectively. Both compounds were spectroscopically and crystallographically characterized. A mechanism involving a 1,2-shift of one of the groups on the azido α-C atom of the cluster-azide intermediate conceited with the photoexpulsion of dinitrogen of the azido ligand is invoked to rationalize the formation of the imino complexes. Density functional theory calculations showed that a cluster-to-ligand transition was responsible for the absorption that promotes the photodecomposition of the cluster-azide complex.

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ER -

Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re₆(μ₃-Se) ₈]²⁺ core-containing clusters

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CCDC 801297: Experimental Crystal Structure Determination

CCDC 801296: Experimental Crystal Structure Determination

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Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re6(μ3-Se) 8]2+ core-containing clusters

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CCDC 801297: Experimental Crystal Structure Determination

CCDC 801296: Experimental Crystal Structure Determination

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Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re₆(μ₃-Se) ₈]²⁺ core-containing clusters