Synthetic Studies on the CpRu-PPh3-(Se2) System: Redox Interconversions of Ru2(Se2)2 Cores

Jayantha Amarasekera; Eric J. Houser; Thomas B. Rauchfuss; Charlotte L. Stern

doi:10.1021/ic00035a018

Synthetic Studies on the CpRu-PPh₃-(Se₂) System: Redox Interconversions of Ru₂(Se₂)₂ Cores

Jayantha Amarasekera
, Eric J. Houser
, Thomas B. Rauchfuss
, Charlotte L. Stern

Chemistry

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

Abstract

The reaction of NaSeH and CpRu(PPh₃)₂Cl gave CpRu(PPh₃)₂SeH, while the synthesis of (MeCp)Ru(PPh₃)₂SeH required the use of NMe₄SeH. The corresponding H₂Se complexes could not be prepared, as CpRu(PPh₃)₂OTf failed to add H₂Se and protonation of (MeCp)Ru(PPh₃)₂SeH gave (MeCp)Ru(PPh₃)₂H₂⁺. The reaction of CpRu(PPh₃)₂OTf with elemental selenium gave [CpRu(PPh₃)₂]₂(μ-η ¹,η¹-Se₂)(OTf)₂ (1). The compound 1·PhMe·CH₂Cl₂ crystallized in the monoclinic space group P2₁, with a = 15.965 (3) Å, b = 15.898 (5) Å, c = 18.406 (4) Å, α = γ = 90°, β = 111.28 (2)°, V = 4353 (3) Å³, and Z = 2. The structure was refined to R = 0.054 (R_w = 0.061). The crystallographic studies provide evidence for Ru-Se multiple bonding but show that the Ru₂Se₂ core is not planar, unlike the core of the analogous persulfido complex. Solutions of 1 reacted further with selenium to give primarily [CpRu(PPh₃)]₂(μ-η¹,η ²-Se₂)₂(OTf)₂. The analogous MeCp complex (2) was characterized by X-ray crystallography. It crystallizes in the triclinic space group P1, with a = 10.909 (5) Å, b = 13.530 (5) Å, c = 10.064 (4) Å, α = 110.13 (3)°, β = 112.18 (3)°, γ = 79.62 (3)°, V = 1289 (2) A³, and Z = 1. The structure was refined to R = 0.050 (R_w = 0.058). Compound 2 was reduced by Cp₂Co to give the unstable compound [(MeCp)Ru(PPh₃)]₂(μ-η¹,η ¹-Se₂)₂, which could be reoxidized to give 2 and which in turn thermally eliminated SePPh₃ to give (MeCp)₄Ru₄Se₄.

Original language	English (US)
Pages (from-to)	1614-1620
Number of pages	7
Journal	Inorganic Chemistry
Volume	31
Issue number	9
DOIs	https://doi.org/10.1021/ic00035a018
State	Published - Apr 1 1992

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{68705896ad3a4c93a096a3da437c364c,

title = "Synthetic Studies on the CpRu-PPh3-(Se2) System: Redox Interconversions of Ru2(Se2)2 Cores",

abstract = "The reaction of NaSeH and CpRu(PPh3)2Cl gave CpRu(PPh3)2SeH, while the synthesis of (MeCp)Ru(PPh3)2SeH required the use of NMe4SeH. The corresponding H2Se complexes could not be prepared, as CpRu(PPh3)2OTf failed to add H2Se and protonation of (MeCp)Ru(PPh3)2SeH gave (MeCp)Ru(PPh3)2H2+. The reaction of CpRu(PPh3)2OTf with elemental selenium gave [CpRu(PPh3)2]2(μ-η 1,η1-Se2)(OTf)2 (1). The compound 1·PhMe·CH2Cl2 crystallized in the monoclinic space group P21, with a = 15.965 (3) {\AA}, b = 15.898 (5) {\AA}, c = 18.406 (4) {\AA}, α = γ = 90°, β = 111.28 (2)°, V = 4353 (3) {\AA}3, and Z = 2. The structure was refined to R = 0.054 (Rw = 0.061). The crystallographic studies provide evidence for Ru-Se multiple bonding but show that the Ru2Se2 core is not planar, unlike the core of the analogous persulfido complex. Solutions of 1 reacted further with selenium to give primarily [CpRu(PPh3)]2(μ-η1,η 2-Se2)2(OTf)2. The analogous MeCp complex (2) was characterized by X-ray crystallography. It crystallizes in the triclinic space group P1, with a = 10.909 (5) {\AA}, b = 13.530 (5) {\AA}, c = 10.064 (4) {\AA}, α = 110.13 (3)°, β = 112.18 (3)°, γ = 79.62 (3)°, V = 1289 (2) A3, and Z = 1. The structure was refined to R = 0.050 (Rw = 0.058). Compound 2 was reduced by Cp2Co to give the unstable compound [(MeCp)Ru(PPh3)]2(μ-η1,η 1-Se2)2, which could be reoxidized to give 2 and which in turn thermally eliminated SePPh3 to give (MeCp)4Ru4Se4.",

author = "Jayantha Amarasekera and Houser, \{Eric J.\} and Rauchfuss, \{Thomas B.\} and Stern, \{Charlotte L.\}",

year = "1992",

month = apr,

day = "1",

doi = "10.1021/ic00035a018",

language = "English (US)",

volume = "31",

pages = "1614--1620",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "9",

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TY - JOUR

T1 - Synthetic Studies on the CpRu-PPh3-(Se2) System

T2 - Redox Interconversions of Ru2(Se2)2 Cores

AU - Amarasekera, Jayantha

AU - Houser, Eric J.

AU - Rauchfuss, Thomas B.

AU - Stern, Charlotte L.

PY - 1992/4/1

Y1 - 1992/4/1

N2 - The reaction of NaSeH and CpRu(PPh3)2Cl gave CpRu(PPh3)2SeH, while the synthesis of (MeCp)Ru(PPh3)2SeH required the use of NMe4SeH. The corresponding H2Se complexes could not be prepared, as CpRu(PPh3)2OTf failed to add H2Se and protonation of (MeCp)Ru(PPh3)2SeH gave (MeCp)Ru(PPh3)2H2+. The reaction of CpRu(PPh3)2OTf with elemental selenium gave [CpRu(PPh3)2]2(μ-η 1,η1-Se2)(OTf)2 (1). The compound 1·PhMe·CH2Cl2 crystallized in the monoclinic space group P21, with a = 15.965 (3) Å, b = 15.898 (5) Å, c = 18.406 (4) Å, α = γ = 90°, β = 111.28 (2)°, V = 4353 (3) Å3, and Z = 2. The structure was refined to R = 0.054 (Rw = 0.061). The crystallographic studies provide evidence for Ru-Se multiple bonding but show that the Ru2Se2 core is not planar, unlike the core of the analogous persulfido complex. Solutions of 1 reacted further with selenium to give primarily [CpRu(PPh3)]2(μ-η1,η 2-Se2)2(OTf)2. The analogous MeCp complex (2) was characterized by X-ray crystallography. It crystallizes in the triclinic space group P1, with a = 10.909 (5) Å, b = 13.530 (5) Å, c = 10.064 (4) Å, α = 110.13 (3)°, β = 112.18 (3)°, γ = 79.62 (3)°, V = 1289 (2) A3, and Z = 1. The structure was refined to R = 0.050 (Rw = 0.058). Compound 2 was reduced by Cp2Co to give the unstable compound [(MeCp)Ru(PPh3)]2(μ-η1,η 1-Se2)2, which could be reoxidized to give 2 and which in turn thermally eliminated SePPh3 to give (MeCp)4Ru4Se4.

AB - The reaction of NaSeH and CpRu(PPh3)2Cl gave CpRu(PPh3)2SeH, while the synthesis of (MeCp)Ru(PPh3)2SeH required the use of NMe4SeH. The corresponding H2Se complexes could not be prepared, as CpRu(PPh3)2OTf failed to add H2Se and protonation of (MeCp)Ru(PPh3)2SeH gave (MeCp)Ru(PPh3)2H2+. The reaction of CpRu(PPh3)2OTf with elemental selenium gave [CpRu(PPh3)2]2(μ-η 1,η1-Se2)(OTf)2 (1). The compound 1·PhMe·CH2Cl2 crystallized in the monoclinic space group P21, with a = 15.965 (3) Å, b = 15.898 (5) Å, c = 18.406 (4) Å, α = γ = 90°, β = 111.28 (2)°, V = 4353 (3) Å3, and Z = 2. The structure was refined to R = 0.054 (Rw = 0.061). The crystallographic studies provide evidence for Ru-Se multiple bonding but show that the Ru2Se2 core is not planar, unlike the core of the analogous persulfido complex. Solutions of 1 reacted further with selenium to give primarily [CpRu(PPh3)]2(μ-η1,η 2-Se2)2(OTf)2. The analogous MeCp complex (2) was characterized by X-ray crystallography. It crystallizes in the triclinic space group P1, with a = 10.909 (5) Å, b = 13.530 (5) Å, c = 10.064 (4) Å, α = 110.13 (3)°, β = 112.18 (3)°, γ = 79.62 (3)°, V = 1289 (2) A3, and Z = 1. The structure was refined to R = 0.050 (Rw = 0.058). Compound 2 was reduced by Cp2Co to give the unstable compound [(MeCp)Ru(PPh3)]2(μ-η1,η 1-Se2)2, which could be reoxidized to give 2 and which in turn thermally eliminated SePPh3 to give (MeCp)4Ru4Se4.

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