Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru3(μ3-η 3-EtSCCRCR)(CO)9(R = Me or Ph) to Ru3(μ-SEt)(CO)g(μ3-η3-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9

Joseph W. Ziller; David K. Bower; Dennis M. Dalton; Jerome B. Keister; Melvyn Rowen Churchill

doi:10.1021/om00104a034

Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru₃(μ₃-η ³-EtSCCRCR)(CO)₉(R = Me or Ph) to Ru₃(μ-SEt)(CO)_g(μ₃-η³-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru₃(μ-SEt)(μ₃-η³-CCPhCHPh)(CO)₉

Joseph W. Ziller
, David K. Bower
, Dennis M. Dalton
, Jerome B. Keister
, Melvyn Rowen Churchill

Chemistry

SUNY Buffalo

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

22 Scopus citations

Abstract

The reaction of (μ-H)₃Ru₃(μ3-CSEt)(CO)₉ with alkynes C2R2 (R = Me or Ph) gives two isomeric alkylidyne-alkyne coupled products: (μ-H)Ru_s(μ₃-η³-EtSCCRCR)(CO)₉, containing a 1, 3-dimetalloallyl ligand, and Ru₃(μ-SEt)(μ₃-η³-CCRCHR)(CO)₉, containing a 1, 1-dimetalloallyl ligand. All clusters were characterized by spectroscopic methods; additionally, the structure of Ru₃(μ-SEt)(μ₃-η³-CCPhCHPh)(CO)₉ was determined by X-ray crystallography. Ru₃(μ-SEt)(μ₃-η³-CCPhCHPh)(CO)₉ crystallizes in the centrosymmetric triclinic space group PI, with a = 10.0719 (13) Å, b = 11.6576 (15) Å, c = 13.1047 (17) Å, α= 78.319 (11)°, β= 76.647 (10)°, γ= 76.225 (11)°, V = 1436.2 (2) Å³, and Z = 2. Diffraction data (Mo Kα, 2θ= 4.0-45.0°) were collected with a Syntex P2₁ diffractometer, and the structure was solved and refined to R_F = 5.5% and Rwf= 3.7% for 3774 data (R_F= 2.9%, R_wF = 3.0% for those 2702 reflections with |F₀| > 6.0σ(|_Fo|)). The molecule is a 50-electron cluster with Ru(1)-Ru(2) = 2.759 (1) A, Ru(1)-Ru(3) = 2.887 (1) Å, and zRu(2)-Ru(1)-Ru(3) = 90.72 (2)°. Each ruthenium atom bears three CO ligands. The μ-SEt ligand bridges two Ru atoms with Ru(1)-S = 2.433 (2) Å, Ru(2)-S = 2.376 (2) A, and zRu(1)-S-Ru(2) = 69.99 (5)°. The μ_3-η³-CC(Ph)CHPh ligand is σ-bonded to Ru(1) and Ru(2) (Ru(1)-C(1) = 2.188 (6) Å and Ru(2)-C(1) = 2.039 (6) Å) and is bonded via an η³-allyl system to Ru(3) [Ru(3)-C(1) = 2.155 (6) Å, Ru(3)-C(4) = 2.225 (6) Å, Ru(3)-C(5) = 2.250 (6) Å, and zC(1)-C(4)-C(5) = 117.6 (6)°]. (μ-H)Ru₃(μ₃-η³-EtSCCRCR)(CO)₉ isomerizes to Ru₃₍μ-SEt)(μ₃-η³-CCRCHR)(CO)₉ in quantitative yield with a first-order rate law (k, 7.9 X 10^-5 s^-1(R = Me) at 60 °C). The isomerization of (μ-H)Ru₃(μ₃-η³-EtSCCRCR)(CO)₉ to Ru₃(μ-SEt)(μ₃-η³-CCRCHR)(CO)₉ involves two of the steps that occur during the related hydrogenation of (μ-H)Ru₃-(μ₃-η³-XCCRCR)(CO)₉ (X = OMe or SEt) to (μ-H)₃Ru3(μ₃-CCHRCH₂R)(CO)₉. Hydrogenation of Ru₃-(μ₃-SEt)(μ₃-η³-CCMeCHMe)(CO)₉(4 atm, 70 °C) forms (μ-H)₃Ru₃(μ₃-CCHMeCH₂Me)(CO)₉(4%) and (μ-H)Ru₃(μ-SEt)(CO)₁₀(51%). The overall conversion of (μ-H)₃Ru₃(μ₃-CSEt)(CO)₉ to (μ-H)3ru3(μ3-cchrch₂R')(CO)₉ is an example of cluster-centered hydrocarbon chain growth.

Original language	English
Pages (from-to)	492-497
Number of pages	6
Journal	Organometallics
Volume	8
Issue number	2
DOIs	https://doi.org/10.1021/om00104a034
State	Published - Feb 1989

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Ziller, J. W., Bower, D. K., Dalton, D. M., Keister, J. B., & Churchill, M. R. (1989). Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru₃(μ₃-η ³-EtSCCRCR)(CO)₉(R = Me or Ph) to Ru₃(μ-SEt)(CO)_g(μ₃-η³-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru₃(μ-SEt)(μ₃-η³-CCPhCHPh)(CO)₉. Organometallics, 8(2), 492-497. https://doi.org/10.1021/om00104a034

Ziller, Joseph W. ; Bower, David K. ; Dalton, Dennis M. et al. / Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru₃(μ₃-η ³-EtSCCRCR)(CO)₉(R = Me or Ph) to Ru₃(μ-SEt)(CO)_g(μ₃-η³-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru₃(μ-SEt)(μ₃-η³-CCPhCHPh)(CO)₉. In: Organometallics. 1989 ; Vol. 8, No. 2. pp. 492-497.

@article{21b21c744f434feb844de9f30d11daa9,

title = "Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru3(μ3-η 3-EtSCCRCR)(CO)9(R = Me or Ph) to Ru3(μ-SEt)(CO)g(μ3-η3-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9",

abstract = "The reaction of (μ-H)3Ru3(μ3-CSEt)(CO)9 with alkynes C2R2 (R = Me or Ph) gives two isomeric alkylidyne-alkyne coupled products: (μ-H)Rus(μ3-η3-EtSCCRCR)(CO)9, containing a 1, 3-dimetalloallyl ligand, and Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9, containing a 1, 1-dimetalloallyl ligand. All clusters were characterized by spectroscopic methods; additionally, the structure of Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9 was determined by X-ray crystallography. Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9 crystallizes in the centrosymmetric triclinic space group PI, with a = 10.0719 (13) {\AA}, b = 11.6576 (15) {\AA}, c = 13.1047 (17) {\AA}, α= 78.319 (11)°, β= 76.647 (10)°, γ= 76.225 (11)°, V = 1436.2 (2) {\AA}3, and Z = 2. Diffraction data (Mo Kα, 2θ= 4.0-45.0°) were collected with a Syntex P21 diffractometer, and the structure was solved and refined to RF = 5.5\% and Rwf= 3.7\% for 3774 data (RF= 2.9\%, RwF = 3.0\% for those 2702 reflections with |F0| > 6.0σ(|Fo|)). The molecule is a 50-electron cluster with Ru(1)-Ru(2) = 2.759 (1) A, Ru(1)-Ru(3) = 2.887 (1) {\AA}, and zRu(2)-Ru(1)-Ru(3) = 90.72 (2)°. Each ruthenium atom bears three CO ligands. The μ-SEt ligand bridges two Ru atoms with Ru(1)-S = 2.433 (2) {\AA}, Ru(2)-S = 2.376 (2) A, and zRu(1)-S-Ru(2) = 69.99 (5)°. The μ3-η3-CC(Ph)CHPh ligand is σ-bonded to Ru(1) and Ru(2) (Ru(1)-C(1) = 2.188 (6) {\AA} and Ru(2)-C(1) = 2.039 (6) {\AA}) and is bonded via an η3-allyl system to Ru(3) [Ru(3)-C(1) = 2.155 (6) {\AA}, Ru(3)-C(4) = 2.225 (6) {\AA}, Ru(3)-C(5) = 2.250 (6) {\AA}, and zC(1)-C(4)-C(5) = 117.6 (6)°]. (μ-H)Ru3(μ3-η3-EtSCCRCR)(CO)9 isomerizes to Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9 in quantitative yield with a first-order rate law (k, 7.9 X 10-5 s-1(R = Me) at 60 °C). The isomerization of (μ-H)Ru3(μ3-η3-EtSCCRCR)(CO)9 to Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9 involves two of the steps that occur during the related hydrogenation of (μ-H)Ru3-(μ3-η3-XCCRCR)(CO)9 (X = OMe or SEt) to (μ-H)3Ru3(μ3-CCHRCH2R)(CO)9. Hydrogenation of Ru3-(μ3-SEt)(μ3-η3-CCMeCHMe)(CO)9(4 atm, 70 °C) forms (μ-H)3Ru3(μ3-CCHMeCH2Me)(CO)9(4\%) and (μ-H)Ru3(μ-SEt)(CO)10(51\%). The overall conversion of (μ-H)3Ru3(μ3-CSEt)(CO)9 to (μ-H)3ru3(μ3-cchrch2R')(CO)9 is an example of cluster-centered hydrocarbon chain growth.",

author = "Ziller, \{Joseph W.\} and Bower, \{David K.\} and Dalton, \{Dennis M.\} and Keister, \{Jerome B.\} and Churchill, \{Melvyn Rowen\}",

year = "1989",

month = feb,

doi = "10.1021/om00104a034",

language = "English",

volume = "8",

pages = "492--497",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

Ziller, JW, Bower, DK, Dalton, DM, Keister, JB & Churchill, MR 1989, 'Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru₃(μ₃-η ³-EtSCCRCR)(CO)₉(R = Me or Ph) to Ru₃(μ-SEt)(CO)_g(μ₃-η³-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru₃(μ-SEt)(μ₃-η³-CCPhCHPh)(CO)₉', Organometallics, vol. 8, no. 2, pp. 492-497. https://doi.org/10.1021/om00104a034

Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru₃(μ₃-η ³-EtSCCRCR)(CO)₉(R = Me or Ph) to Ru₃(μ-SEt)(CO)_g(μ₃-η³-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru₃(μ-SEt)(μ₃-η³-CCPhCHPh)(CO)₉. / Ziller, Joseph W.; Bower, David K.; Dalton, Dennis M. et al.
In: Organometallics, Vol. 8, No. 2, 02.1989, p. 492-497.

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

TY - JOUR

T1 - Alkylidyne-Alkyne Coupling on Triruthenium Clusters. Isomerization of (μ-H)Ru3(μ3-η 3-EtSCCRCR)(CO)9(R = Me or Ph) to Ru3(μ-SEt)(CO)g(μ3-η3-CCRCHR), an Intermediate in Alkylidyne Chain Growth. The Crystal Structure of Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9

AU - Ziller, Joseph W.

AU - Bower, David K.

AU - Dalton, Dennis M.

AU - Keister, Jerome B.

AU - Churchill, Melvyn Rowen

PY - 1989/2

Y1 - 1989/2

N2 - The reaction of (μ-H)3Ru3(μ3-CSEt)(CO)9 with alkynes C2R2 (R = Me or Ph) gives two isomeric alkylidyne-alkyne coupled products: (μ-H)Rus(μ3-η3-EtSCCRCR)(CO)9, containing a 1, 3-dimetalloallyl ligand, and Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9, containing a 1, 1-dimetalloallyl ligand. All clusters were characterized by spectroscopic methods; additionally, the structure of Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9 was determined by X-ray crystallography. Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9 crystallizes in the centrosymmetric triclinic space group PI, with a = 10.0719 (13) Å, b = 11.6576 (15) Å, c = 13.1047 (17) Å, α= 78.319 (11)°, β= 76.647 (10)°, γ= 76.225 (11)°, V = 1436.2 (2) Å3, and Z = 2. Diffraction data (Mo Kα, 2θ= 4.0-45.0°) were collected with a Syntex P21 diffractometer, and the structure was solved and refined to RF = 5.5% and Rwf= 3.7% for 3774 data (RF= 2.9%, RwF = 3.0% for those 2702 reflections with |F0| > 6.0σ(|Fo|)). The molecule is a 50-electron cluster with Ru(1)-Ru(2) = 2.759 (1) A, Ru(1)-Ru(3) = 2.887 (1) Å, and zRu(2)-Ru(1)-Ru(3) = 90.72 (2)°. Each ruthenium atom bears three CO ligands. The μ-SEt ligand bridges two Ru atoms with Ru(1)-S = 2.433 (2) Å, Ru(2)-S = 2.376 (2) A, and zRu(1)-S-Ru(2) = 69.99 (5)°. The μ3-η3-CC(Ph)CHPh ligand is σ-bonded to Ru(1) and Ru(2) (Ru(1)-C(1) = 2.188 (6) Å and Ru(2)-C(1) = 2.039 (6) Å) and is bonded via an η3-allyl system to Ru(3) [Ru(3)-C(1) = 2.155 (6) Å, Ru(3)-C(4) = 2.225 (6) Å, Ru(3)-C(5) = 2.250 (6) Å, and zC(1)-C(4)-C(5) = 117.6 (6)°]. (μ-H)Ru3(μ3-η3-EtSCCRCR)(CO)9 isomerizes to Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9 in quantitative yield with a first-order rate law (k, 7.9 X 10-5 s-1(R = Me) at 60 °C). The isomerization of (μ-H)Ru3(μ3-η3-EtSCCRCR)(CO)9 to Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9 involves two of the steps that occur during the related hydrogenation of (μ-H)Ru3-(μ3-η3-XCCRCR)(CO)9 (X = OMe or SEt) to (μ-H)3Ru3(μ3-CCHRCH2R)(CO)9. Hydrogenation of Ru3-(μ3-SEt)(μ3-η3-CCMeCHMe)(CO)9(4 atm, 70 °C) forms (μ-H)3Ru3(μ3-CCHMeCH2Me)(CO)9(4%) and (μ-H)Ru3(μ-SEt)(CO)10(51%). The overall conversion of (μ-H)3Ru3(μ3-CSEt)(CO)9 to (μ-H)3ru3(μ3-cchrch2R')(CO)9 is an example of cluster-centered hydrocarbon chain growth.

AB - The reaction of (μ-H)3Ru3(μ3-CSEt)(CO)9 with alkynes C2R2 (R = Me or Ph) gives two isomeric alkylidyne-alkyne coupled products: (μ-H)Rus(μ3-η3-EtSCCRCR)(CO)9, containing a 1, 3-dimetalloallyl ligand, and Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9, containing a 1, 1-dimetalloallyl ligand. All clusters were characterized by spectroscopic methods; additionally, the structure of Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9 was determined by X-ray crystallography. Ru3(μ-SEt)(μ3-η3-CCPhCHPh)(CO)9 crystallizes in the centrosymmetric triclinic space group PI, with a = 10.0719 (13) Å, b = 11.6576 (15) Å, c = 13.1047 (17) Å, α= 78.319 (11)°, β= 76.647 (10)°, γ= 76.225 (11)°, V = 1436.2 (2) Å3, and Z = 2. Diffraction data (Mo Kα, 2θ= 4.0-45.0°) were collected with a Syntex P21 diffractometer, and the structure was solved and refined to RF = 5.5% and Rwf= 3.7% for 3774 data (RF= 2.9%, RwF = 3.0% for those 2702 reflections with |F0| > 6.0σ(|Fo|)). The molecule is a 50-electron cluster with Ru(1)-Ru(2) = 2.759 (1) A, Ru(1)-Ru(3) = 2.887 (1) Å, and zRu(2)-Ru(1)-Ru(3) = 90.72 (2)°. Each ruthenium atom bears three CO ligands. The μ-SEt ligand bridges two Ru atoms with Ru(1)-S = 2.433 (2) Å, Ru(2)-S = 2.376 (2) A, and zRu(1)-S-Ru(2) = 69.99 (5)°. The μ3-η3-CC(Ph)CHPh ligand is σ-bonded to Ru(1) and Ru(2) (Ru(1)-C(1) = 2.188 (6) Å and Ru(2)-C(1) = 2.039 (6) Å) and is bonded via an η3-allyl system to Ru(3) [Ru(3)-C(1) = 2.155 (6) Å, Ru(3)-C(4) = 2.225 (6) Å, Ru(3)-C(5) = 2.250 (6) Å, and zC(1)-C(4)-C(5) = 117.6 (6)°]. (μ-H)Ru3(μ3-η3-EtSCCRCR)(CO)9 isomerizes to Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9 in quantitative yield with a first-order rate law (k, 7.9 X 10-5 s-1(R = Me) at 60 °C). The isomerization of (μ-H)Ru3(μ3-η3-EtSCCRCR)(CO)9 to Ru3(μ-SEt)(μ3-η3-CCRCHR)(CO)9 involves two of the steps that occur during the related hydrogenation of (μ-H)Ru3-(μ3-η3-XCCRCR)(CO)9 (X = OMe or SEt) to (μ-H)3Ru3(μ3-CCHRCH2R)(CO)9. Hydrogenation of Ru3-(μ3-SEt)(μ3-η3-CCMeCHMe)(CO)9(4 atm, 70 °C) forms (μ-H)3Ru3(μ3-CCHMeCH2Me)(CO)9(4%) and (μ-H)Ru3(μ-SEt)(CO)10(51%). The overall conversion of (μ-H)3Ru3(μ3-CSEt)(CO)9 to (μ-H)3ru3(μ3-cchrch2R')(CO)9 is an example of cluster-centered hydrocarbon chain growth.

UR - https://www.scopus.com/pages/publications/0038550752

U2 - 10.1021/om00104a034

DO - 10.1021/om00104a034

M3 - Article

AN - SCOPUS:0038550752

SN - 0276-7333

VL - 8

SP - 492

EP - 497

JO - Organometallics

JF - Organometallics

IS - 2

ER -