Synthesis of (μ-H)3RU3(μ3-CSET)(CO)9 and Its Rearrangement To (μ-H)RU3(μ3-≡2-ch2set)(co)9. Crystal Structure of (μ-H)Ru3(μ3-≡2-CH2set) (CO)9

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

doi:10.1021/om00147a020

Synthesis of (μ-H)₃RU3(μ₃-CSET)(CO)₉ and Its Rearrangement To (μ-H)RU₃(μ₃-≡²-ch₂set)(co)₉. Crystal Structure of (μ-H)Ru₃(μ₃-≡²-CH₂set) (CO)₉

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

Chemistry

University at Buffalo

SUNY Buffalo

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

22 Scopus citations

Abstract

(M-H)₃Ru₃(M3-CSEt)(CO)₉ is synthesized by treatment of (A*-H)₃Ru₃0u3-CBr)(CO)₉ with ethanethiol and triethylamine and has been fully characterized by spectroscopic methods. Upon heating at 50–60 °C, (μ-H)₃Ru₃(M3*CSEt)(CO)₉ rearranges to (M-H)Ru₃0u3V-CH₂SEt)(CO)₉(46% yield), characterized by spectroscopy and by X-ray crystallography. (μ-H)Ru₃(ii₃-77²-CH₂SEt)(CO)₉ crystallizes in the centrosymmetric monoclinic space group P2_xjn (No. 14) with a - 8.2639 (10) A, b = 16.8680 (17) A, c = 13.7886 (15) A, (3 - 93.788 (9)°, V = 1917.9 (4) A³, and Z = 4. X-ray diffraction data (Mo Ka, 26 - 4.5-45.0°) were collected with a Syntex P2_X automated four-circle diffractometer, and the structure was refined to R_F= 6.0% for all 2523 unique reflections (Rp = 2.9% for those 1732 reflections with| F₀| > 6cr(|F₀|)). The complex contains a triangular cluster of ruthenium atoms, each of which is linked to three terminal carbonyl ligands. The M₃-7²-CH₂SEt ligand caps the triruthenium cluster with the sulfur atom bridging Ru(2) and Ru(3) [Ru(2)-S = 2.348 (2) A, Ru(3)-S = 2.302 (2) A, and Ru(2)-S-Ru(3) = 73.07 (7)°] and with the methylene carbon atom, C(l), bonded to Ru(l) [Ru(l)-C(l) = 2.188 (9) A]. A hydride ligand bridges the Ru(l)-Ru(2) edge in the equatorial plane, with Ru(l)-H(12) = 1.61 (7), Ru(2)-H(12) = 1.87 (7) A, and Ru(l)-H(12)-Ru(2) = 117 (4)°. The Ru-Ru bond distances are inequivalent [Ru(l)-Ru(2) = 2.974 (1), Ru(l)-Ru(3) = 2.818 (1), and Ru(2)-Ru(3) = 2.769 (1) A], with the edge bridged by the hydride ligand having the longest distance. The rearrangement of (M-H)₃Ru₃0i₃-CSEt) (CO)₉ to (M-H)Ru₃0n₃-7²-CH₂SEt) (CO)₉ involves two C-H reductive eliminations, the two unsaturated metal atoms thus formed being stabilized by coordination of the sulfur atom. Thus, (Ai-H)Ru₃(M3-77²-CH₂SEt)(CO)₉ is a stabilized alkyl analogous to an intermediate in the previously reported “desorption” of CH₃X from (μ-H)₃Ru₃(ji₃-CX)(CO)₉(X = Ph, Cl, or C0₂Me) forming Ru₃(CO)₁₂ under a CO atmosphere.

Original language	English
Pages (from-to)	806-812
Number of pages	7
Journal	Organometallics
Volume	6
Issue number	4
DOIs	https://doi.org/10.1021/om00147a020
State	Published - Apr 1 1987

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@article{9328067c3af042309717e9ec1bf77051,

title = "Synthesis of (μ-H)3RU3(μ3-CSET)(CO)9 and Its Rearrangement To (μ-H)RU3(μ3-≡2-ch2set)(co)9. Crystal Structure of (μ-H)Ru3(μ3-≡2-CH2set) (CO)9",

abstract = "(M-H)3Ru3(M3-CSEt)(CO)9 is synthesized by treatment of (A*-H)3Ru30u3-CBr)(CO)9 with ethanethiol and triethylamine and has been fully characterized by spectroscopic methods. Upon heating at 50–60 °C, (μ-H)3Ru3(M3*CSEt)(CO)9 rearranges to (M-H)Ru30u3V-CH2SEt)(CO)9(46\% yield), characterized by spectroscopy and by X-ray crystallography. (μ-H)Ru3(ii3-772-CH2SEt)(CO)9 crystallizes in the centrosymmetric monoclinic space group P2xjn (No. 14) with a - 8.2639 (10) A, b = 16.8680 (17) A, c = 13.7886 (15) A, (3 - 93.788 (9)°, V = 1917.9 (4) A3, and Z = 4. X-ray diffraction data (Mo Ka, 26 - 4.5-45.0°) were collected with a Syntex P2X automated four-circle diffractometer, and the structure was refined to RF= 6.0\% for all 2523 unique reflections (Rp = 2.9\% for those 1732 reflections with| F0| > 6cr(|F0|)). The complex contains a triangular cluster of ruthenium atoms, each of which is linked to three terminal carbonyl ligands. The M3-72-CH2SEt ligand caps the triruthenium cluster with the sulfur atom bridging Ru(2) and Ru(3) [Ru(2)-S = 2.348 (2) A, Ru(3)-S = 2.302 (2) A, and Ru(2)-S-Ru(3) = 73.07 (7)°] and with the methylene carbon atom, C(l), bonded to Ru(l) [Ru(l)-C(l) = 2.188 (9) A]. A hydride ligand bridges the Ru(l)-Ru(2) edge in the equatorial plane, with Ru(l)-H(12) = 1.61 (7), Ru(2)-H(12) = 1.87 (7) A, and Ru(l)-H(12)-Ru(2) = 117 (4)°. The Ru-Ru bond distances are inequivalent [Ru(l)-Ru(2) = 2.974 (1), Ru(l)-Ru(3) = 2.818 (1), and Ru(2)-Ru(3) = 2.769 (1) A], with the edge bridged by the hydride ligand having the longest distance. The rearrangement of (M-H)3Ru30i3-CSEt) (CO)9 to (M-H)Ru30n3-72-CH2SEt) (CO)9 involves two C-H reductive eliminations, the two unsaturated metal atoms thus formed being stabilized by coordination of the sulfur atom. Thus, (Ai-H)Ru3(M3-772-CH2SEt)(CO)9 is a stabilized alkyl analogous to an intermediate in the previously reported “desorption” of CH3X from (μ-H)3Ru3(ji3-CX)(CO)9(X = Ph, Cl, or C02Me) forming Ru3(CO)12 under a CO atmosphere.",

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

year = "1987",

month = apr,

day = "1",

doi = "10.1021/om00147a020",

language = "English",

volume = "6",

pages = "806--812",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Synthesis of (μ-H)3RU3(μ3-CSET)(CO)9 and Its Rearrangement To (μ-H)RU3(μ3-≡2-ch2set)(co)9. Crystal Structure of (μ-H)Ru3(μ3-≡2-CH2set) (CO)9

AU - Churchill, Melvyn Rowen

AU - Ziller, Joseph W.

AU - Dalton, Dennis M.

AU - Keister, Jerome B.

PY - 1987/4/1

Y1 - 1987/4/1

N2 - (M-H)3Ru3(M3-CSEt)(CO)9 is synthesized by treatment of (A*-H)3Ru30u3-CBr)(CO)9 with ethanethiol and triethylamine and has been fully characterized by spectroscopic methods. Upon heating at 50–60 °C, (μ-H)3Ru3(M3*CSEt)(CO)9 rearranges to (M-H)Ru30u3V-CH2SEt)(CO)9(46% yield), characterized by spectroscopy and by X-ray crystallography. (μ-H)Ru3(ii3-772-CH2SEt)(CO)9 crystallizes in the centrosymmetric monoclinic space group P2xjn (No. 14) with a - 8.2639 (10) A, b = 16.8680 (17) A, c = 13.7886 (15) A, (3 - 93.788 (9)°, V = 1917.9 (4) A3, and Z = 4. X-ray diffraction data (Mo Ka, 26 - 4.5-45.0°) were collected with a Syntex P2X automated four-circle diffractometer, and the structure was refined to RF= 6.0% for all 2523 unique reflections (Rp = 2.9% for those 1732 reflections with| F0| > 6cr(|F0|)). The complex contains a triangular cluster of ruthenium atoms, each of which is linked to three terminal carbonyl ligands. The M3-72-CH2SEt ligand caps the triruthenium cluster with the sulfur atom bridging Ru(2) and Ru(3) [Ru(2)-S = 2.348 (2) A, Ru(3)-S = 2.302 (2) A, and Ru(2)-S-Ru(3) = 73.07 (7)°] and with the methylene carbon atom, C(l), bonded to Ru(l) [Ru(l)-C(l) = 2.188 (9) A]. A hydride ligand bridges the Ru(l)-Ru(2) edge in the equatorial plane, with Ru(l)-H(12) = 1.61 (7), Ru(2)-H(12) = 1.87 (7) A, and Ru(l)-H(12)-Ru(2) = 117 (4)°. The Ru-Ru bond distances are inequivalent [Ru(l)-Ru(2) = 2.974 (1), Ru(l)-Ru(3) = 2.818 (1), and Ru(2)-Ru(3) = 2.769 (1) A], with the edge bridged by the hydride ligand having the longest distance. The rearrangement of (M-H)3Ru30i3-CSEt) (CO)9 to (M-H)Ru30n3-72-CH2SEt) (CO)9 involves two C-H reductive eliminations, the two unsaturated metal atoms thus formed being stabilized by coordination of the sulfur atom. Thus, (Ai-H)Ru3(M3-772-CH2SEt)(CO)9 is a stabilized alkyl analogous to an intermediate in the previously reported “desorption” of CH3X from (μ-H)3Ru3(ji3-CX)(CO)9(X = Ph, Cl, or C02Me) forming Ru3(CO)12 under a CO atmosphere.

AB - (M-H)3Ru3(M3-CSEt)(CO)9 is synthesized by treatment of (A*-H)3Ru30u3-CBr)(CO)9 with ethanethiol and triethylamine and has been fully characterized by spectroscopic methods. Upon heating at 50–60 °C, (μ-H)3Ru3(M3*CSEt)(CO)9 rearranges to (M-H)Ru30u3V-CH2SEt)(CO)9(46% yield), characterized by spectroscopy and by X-ray crystallography. (μ-H)Ru3(ii3-772-CH2SEt)(CO)9 crystallizes in the centrosymmetric monoclinic space group P2xjn (No. 14) with a - 8.2639 (10) A, b = 16.8680 (17) A, c = 13.7886 (15) A, (3 - 93.788 (9)°, V = 1917.9 (4) A3, and Z = 4. X-ray diffraction data (Mo Ka, 26 - 4.5-45.0°) were collected with a Syntex P2X automated four-circle diffractometer, and the structure was refined to RF= 6.0% for all 2523 unique reflections (Rp = 2.9% for those 1732 reflections with| F0| > 6cr(|F0|)). The complex contains a triangular cluster of ruthenium atoms, each of which is linked to three terminal carbonyl ligands. The M3-72-CH2SEt ligand caps the triruthenium cluster with the sulfur atom bridging Ru(2) and Ru(3) [Ru(2)-S = 2.348 (2) A, Ru(3)-S = 2.302 (2) A, and Ru(2)-S-Ru(3) = 73.07 (7)°] and with the methylene carbon atom, C(l), bonded to Ru(l) [Ru(l)-C(l) = 2.188 (9) A]. A hydride ligand bridges the Ru(l)-Ru(2) edge in the equatorial plane, with Ru(l)-H(12) = 1.61 (7), Ru(2)-H(12) = 1.87 (7) A, and Ru(l)-H(12)-Ru(2) = 117 (4)°. The Ru-Ru bond distances are inequivalent [Ru(l)-Ru(2) = 2.974 (1), Ru(l)-Ru(3) = 2.818 (1), and Ru(2)-Ru(3) = 2.769 (1) A], with the edge bridged by the hydride ligand having the longest distance. The rearrangement of (M-H)3Ru30i3-CSEt) (CO)9 to (M-H)Ru30n3-72-CH2SEt) (CO)9 involves two C-H reductive eliminations, the two unsaturated metal atoms thus formed being stabilized by coordination of the sulfur atom. Thus, (Ai-H)Ru3(M3-772-CH2SEt)(CO)9 is a stabilized alkyl analogous to an intermediate in the previously reported “desorption” of CH3X from (μ-H)3Ru3(ji3-CX)(CO)9(X = Ph, Cl, or C02Me) forming Ru3(CO)12 under a CO atmosphere.

UR - https://www.scopus.com/pages/publications/0037536554

U2 - 10.1021/om00147a020

DO - 10.1021/om00147a020

M3 - Article

SN - 0276-7333

VL - 6

SP - 806

EP - 812

JO - Organometallics

JF - Organometallics

IS - 4

ER -

Synthesis of (μ-H)₃RU3(μ₃-CSET)(CO)₉ and Its Rearrangement To (μ-H)RU₃(μ₃-≡²-ch₂set)(co)₉. Crystal Structure of (μ-H)Ru₃(μ₃-≡²-CH₂set) (CO)₉

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