Synthesis and structural characterization of some selenoruthenates and telluroruthenates

Sergey M. Dibrov; Bin Deng; Donald E. Ellis; James A. Ibers

doi:10.1021/ic0483646

Synthesis and structural characterization of some selenoruthenates and telluroruthenates

Sergey M. Dibrov, Bin Deng, Donald E. Ellis, James A. Ibers^*

^*Corresponding author for this work

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Abstract

The reaction of solid [RuClCp(PPh ₃) ₂] with TeSe ₃ ^2- or Se _n ^2- in DMF leads to the formation of [RuCp(PPh ₃)(μ ₂-Se ₂)] ₂ (1). In the structure of this compound the two bridging Se ₂ groups lead to a six-membered Ru ₂Se ₄ ring in a chair conformation. Attached to each Ru center is a PPh ₃ ligand in an equatorial position and a Cp ring in an axial position. The compound is diamagnetic. The compound [Ru ₂Cp ₂(μ ₃-Se ₂)(μ ₃-Se)] ₂ (2) is obtained under similar conditions in the presence of air. This structure comprises a centrosymmetric Ru ₄Se ₆ dimer formed from the two bridging Se groups and the two bridging Se ₂ groups. Each Ru center is π-bonded to a Cp ring. The reaction of solid [RuClCp(PPh ₃) ₂] with a Te _n ^2- polytelluride solution in DMF leads to the diamagnetic compound [(RuCp-(PPh ₃)) ₂(μ ₂-(1,4-η:3,6- η)Te ₆)] (3). Here the Ru centers are bound to a bridging Te ₆ chain at the 1, 4, 3, and 6 positions, leading to a bicyclic Ru ₂Te ₆ ring. Each Ru atom is bound to a Cp ring and a PPh ₃ group. This dimer possesses a center of symmetry. The structure of 3 is the first example of a bicyclic complex where fusion occurs along a Te-Te bond. If the same reaction is carried out in DMF/CH ₂Cl ₂, rather than DMF, then [(RuCp(PPh ₃)) ₂-(μ2- (1,4-η:3,6-η)Te ₆)]·CH ₂Cl ₂ (4) is obtained. In the solid state it possesses the same Ru ₂Te ₆ structural unit as does 3, but the unit lacks a crystallographically imposed center of symmetry. The electronic structures of 3 and 4 have been analyzed with the use of first principles density functional theory. Bond order analysis indicates that the Te-Te bond where fusion occurs has a shared bonding charge of about 2/3 of that found for Te-Te single bonds.

Original language	English (US)
Pages (from-to)	3441-3448
Number of pages	8
Journal	Inorganic chemistry
Volume	44
Issue number	10
DOIs	https://doi.org/10.1021/ic0483646
State	Published - May 16 2005

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{839dc2d1fef846a5b13ca2866844674a,

title = "Synthesis and structural characterization of some selenoruthenates and telluroruthenates",

abstract = "The reaction of solid [RuClCp(PPh 3) 2] with TeSe 3 2- or Se n 2- in DMF leads to the formation of [RuCp(PPh 3)(μ 2-Se 2)] 2 (1). In the structure of this compound the two bridging Se 2 groups lead to a six-membered Ru 2Se 4 ring in a chair conformation. Attached to each Ru center is a PPh 3 ligand in an equatorial position and a Cp ring in an axial position. The compound is diamagnetic. The compound [Ru 2Cp 2(μ 3-Se 2)(μ 3-Se)] 2 (2) is obtained under similar conditions in the presence of air. This structure comprises a centrosymmetric Ru 4Se 6 dimer formed from the two bridging Se groups and the two bridging Se 2 groups. Each Ru center is π-bonded to a Cp ring. The reaction of solid [RuClCp(PPh 3) 2] with a Te n 2- polytelluride solution in DMF leads to the diamagnetic compound [(RuCp-(PPh 3)) 2(μ 2-(1,4-η:3,6- η)Te 6)] (3). Here the Ru centers are bound to a bridging Te 6 chain at the 1, 4, 3, and 6 positions, leading to a bicyclic Ru 2Te 6 ring. Each Ru atom is bound to a Cp ring and a PPh 3 group. This dimer possesses a center of symmetry. The structure of 3 is the first example of a bicyclic complex where fusion occurs along a Te-Te bond. If the same reaction is carried out in DMF/CH 2Cl 2, rather than DMF, then [(RuCp(PPh 3)) 2-(μ2- (1,4-η:3,6-η)Te 6)]·CH 2Cl 2 (4) is obtained. In the solid state it possesses the same Ru 2Te 6 structural unit as does 3, but the unit lacks a crystallographically imposed center of symmetry. The electronic structures of 3 and 4 have been analyzed with the use of first principles density functional theory. Bond order analysis indicates that the Te-Te bond where fusion occurs has a shared bonding charge of about 2/3 of that found for Te-Te single bonds.",

author = "Dibrov, {Sergey M.} and Bin Deng and Ellis, {Donald E.} and Ibers, {James A.}",

year = "2005",

month = may,

day = "16",

doi = "10.1021/ic0483646",

language = "English (US)",

volume = "44",

pages = "3441--3448",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

T1 - Synthesis and structural characterization of some selenoruthenates and telluroruthenates

AU - Dibrov, Sergey M.

AU - Deng, Bin

AU - Ellis, Donald E.

AU - Ibers, James A.

PY - 2005/5/16

Y1 - 2005/5/16

N2 - The reaction of solid [RuClCp(PPh 3) 2] with TeSe 3 2- or Se n 2- in DMF leads to the formation of [RuCp(PPh 3)(μ 2-Se 2)] 2 (1). In the structure of this compound the two bridging Se 2 groups lead to a six-membered Ru 2Se 4 ring in a chair conformation. Attached to each Ru center is a PPh 3 ligand in an equatorial position and a Cp ring in an axial position. The compound is diamagnetic. The compound [Ru 2Cp 2(μ 3-Se 2)(μ 3-Se)] 2 (2) is obtained under similar conditions in the presence of air. This structure comprises a centrosymmetric Ru 4Se 6 dimer formed from the two bridging Se groups and the two bridging Se 2 groups. Each Ru center is π-bonded to a Cp ring. The reaction of solid [RuClCp(PPh 3) 2] with a Te n 2- polytelluride solution in DMF leads to the diamagnetic compound [(RuCp-(PPh 3)) 2(μ 2-(1,4-η:3,6- η)Te 6)] (3). Here the Ru centers are bound to a bridging Te 6 chain at the 1, 4, 3, and 6 positions, leading to a bicyclic Ru 2Te 6 ring. Each Ru atom is bound to a Cp ring and a PPh 3 group. This dimer possesses a center of symmetry. The structure of 3 is the first example of a bicyclic complex where fusion occurs along a Te-Te bond. If the same reaction is carried out in DMF/CH 2Cl 2, rather than DMF, then [(RuCp(PPh 3)) 2-(μ2- (1,4-η:3,6-η)Te 6)]·CH 2Cl 2 (4) is obtained. In the solid state it possesses the same Ru 2Te 6 structural unit as does 3, but the unit lacks a crystallographically imposed center of symmetry. The electronic structures of 3 and 4 have been analyzed with the use of first principles density functional theory. Bond order analysis indicates that the Te-Te bond where fusion occurs has a shared bonding charge of about 2/3 of that found for Te-Te single bonds.

AB - The reaction of solid [RuClCp(PPh 3) 2] with TeSe 3 2- or Se n 2- in DMF leads to the formation of [RuCp(PPh 3)(μ 2-Se 2)] 2 (1). In the structure of this compound the two bridging Se 2 groups lead to a six-membered Ru 2Se 4 ring in a chair conformation. Attached to each Ru center is a PPh 3 ligand in an equatorial position and a Cp ring in an axial position. The compound is diamagnetic. The compound [Ru 2Cp 2(μ 3-Se 2)(μ 3-Se)] 2 (2) is obtained under similar conditions in the presence of air. This structure comprises a centrosymmetric Ru 4Se 6 dimer formed from the two bridging Se groups and the two bridging Se 2 groups. Each Ru center is π-bonded to a Cp ring. The reaction of solid [RuClCp(PPh 3) 2] with a Te n 2- polytelluride solution in DMF leads to the diamagnetic compound [(RuCp-(PPh 3)) 2(μ 2-(1,4-η:3,6- η)Te 6)] (3). Here the Ru centers are bound to a bridging Te 6 chain at the 1, 4, 3, and 6 positions, leading to a bicyclic Ru 2Te 6 ring. Each Ru atom is bound to a Cp ring and a PPh 3 group. This dimer possesses a center of symmetry. The structure of 3 is the first example of a bicyclic complex where fusion occurs along a Te-Te bond. If the same reaction is carried out in DMF/CH 2Cl 2, rather than DMF, then [(RuCp(PPh 3)) 2-(μ2- (1,4-η:3,6-η)Te 6)]·CH 2Cl 2 (4) is obtained. In the solid state it possesses the same Ru 2Te 6 structural unit as does 3, but the unit lacks a crystallographically imposed center of symmetry. The electronic structures of 3 and 4 have been analyzed with the use of first principles density functional theory. Bond order analysis indicates that the Te-Te bond where fusion occurs has a shared bonding charge of about 2/3 of that found for Te-Te single bonds.

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U2 - 10.1021/ic0483646

DO - 10.1021/ic0483646

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 10

ER -

Synthesis and structural characterization of some selenoruthenates and telluroruthenates

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