Synthesis of Cyclohexadiene Complexes of (Methylidyne)triruthenium Clusters. The Crystal Structure of (μ-H)Ru3(μ3-COCH3)(CO)8(1,3-C6H8) and a Redetermination of the Structure of (μ-H)Ru3(μ-COCH3)(CO)10

Melvyn Rowen Churchill; Lawrence R. Beanan; Harvey J. Wasserman; Clifford Bueno; Zuraidah Abdul Rahman; Jerome B. Keister

doi:10.1021/om50003a019

Synthesis of Cyclohexadiene Complexes of (Methylidyne)triruthenium Clusters. The Crystal Structure of (μ-H)Ru₃(μ₃-COCH₃)(CO)₈(1,3-C₆H₈) and a Redetermination of the Structure of (μ-H)Ru₃(μ-COCH₃)(CO)₁₀

Melvyn Rowen Churchill
, Lawrence R. Beanan
, Harvey J. Wasserman
, Clifford Bueno
, Zuraidah Abdul Rahman
, Jerome B. Keister

Chemistry

University at Buffalo

SUNY Buffalo

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

41 Scopus citations

Abstract

The complexes Gi-H)Ru₃(μ₃-CX)(CO)8(l,3-cyclohexadiene) (1, X = OMe; ₂, X = Ph) are formed by reactions of the corresponding (μ-H)₃Ru₃(μ₃-CX)(CO)₉ with alkenes in the presence of excess 1,3-cyclohexadiene; 1 equiv of the hydrogenated alkene is also formed. The clusters 1 and 2 have been characterized spectroscopically, and the crystal structure of 1 has been determined by a complete three-dimensional X-ray crystallographic analysis. Because the structure of 1 differs significantly from that of the parent carbonyl (μ-H)Ru₃(μ-COMe)(CO)₁₀, a redetermination of the structure of the latter has also been performed. The complex (μ-H)Ru₃(μ-COMe)(CO)₁₀ crystallizes in the monoclinic space group P2₁/c with a = 7.9689 (17) Å,b = 17.0158 (42) Å, c = 14.1216 (30) Å, β = 104.082 (17), and Z = 4. Diffraction data were collected with a Syntex P2₁ diffractometer and refined to RF = 2.6% for all 2444 data with 2θ(Mo Kα) = 3.5-45.0. The molecule contains a triangular array of ruthenium atoms; four terminal carbonyl ligands are associated with Ru(3), while Ru(l) and Ru(2) are each linked to three. In addition, Ru(l) and Ru(2) are bridged by a hydride ligand and by an μ-COMe ligand. (μ-H)Ru₃(μ₃-COMe)(CO)₈(l,₃-C₆H₈) (1) crystallizes in the triclinic space group P1 with a = 7.4916 (17) Å, b = 8.7077 (19) Å, c = 15.6023 (32) Å, α = 89.995 (17)β = 97.832 (17γ = 98.991 (18)Z = 2. Data for 2θ(Mo Kα) = 4.0-50.0 were collected, and the structure was refined to RF = 2.3% for all 3528 reflections. This molecule contains a triangular array of ruthenium atoms capped by a μ3-COMe ligand. There are three terminal carbonyl ligands each on Ru(l) and Ru(₃), which are bridged by a hydride ligand; Ru(₂) is linked to an)η4-l,3-cyclohexadiene ligand and bonded to two carbonyl ligands (which are weakly “semibridging” to Ru(l) and Ru(3)). A comparison of the structures of 1 and those of (μ-H)M₃(μ-CX)(CO)₁₀ (M = Fe, Ru, X = O^-, NMe2, OMe; M = Os, X = H, NH-t-Bu), which have been determined previously, reveals that the coordination geometry adopted by the methylidyne moiety varies in a systematic manner with (i) the metal, (ii) the methylidyne substituent, and (iii) the other ligands of the cluster. These trends may have implications for the geometry adopted by alkylidyne fragments bound to metal surfaces.

Original language	English
Pages (from-to)	1179-1186
Number of pages	8
Journal	Organometallics
Volume	2
Issue number	9
DOIs	https://doi.org/10.1021/om50003a019
State	Published - Sep 1983

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Churchill, M. R., Beanan, L. R., Wasserman, H. J., Bueno, C., Rahman, Z. A., & Keister, J. B. (1983). Synthesis of Cyclohexadiene Complexes of (Methylidyne)triruthenium Clusters. The Crystal Structure of (μ-H)Ru₃(μ₃-COCH₃)(CO)₈(1,3-C₆H₈) and a Redetermination of the Structure of (μ-H)Ru₃(μ-COCH₃)(CO)₁₀. Organometallics, 2(9), 1179-1186. https://doi.org/10.1021/om50003a019

@article{33a29400feef465182ae1b82656dc7b5,

title = "Synthesis of Cyclohexadiene Complexes of (Methylidyne)triruthenium Clusters. The Crystal Structure of (μ-H)Ru3(μ3-COCH3)(CO)8(1,3-C6H8) and a Redetermination of the Structure of (μ-H)Ru3(μ-COCH3)(CO)10",

abstract = "The complexes Gi-H)Ru3(μ3-CX)(CO)8(l,3-cyclohexadiene) (1, X = OMe; 2, X = Ph) are formed by reactions of the corresponding (μ-H)3Ru3(μ3-CX)(CO)9 with alkenes in the presence of excess 1,3-cyclohexadiene; 1 equiv of the hydrogenated alkene is also formed. The clusters 1 and 2 have been characterized spectroscopically, and the crystal structure of 1 has been determined by a complete three-dimensional X-ray crystallographic analysis. Because the structure of 1 differs significantly from that of the parent carbonyl (μ-H)Ru3(μ-COMe)(CO)10, a redetermination of the structure of the latter has also been performed. The complex (μ-H)Ru3(μ-COMe)(CO)10 crystallizes in the monoclinic space group P21/c with a = 7.9689 (17) {\AA},b = 17.0158 (42) {\AA}, c = 14.1216 (30) {\AA}, β = 104.082 (17), and Z = 4. Diffraction data were collected with a Syntex P21 diffractometer and refined to RF = 2.6\% for all 2444 data with 2θ(Mo Kα) = 3.5-45.0. The molecule contains a triangular array of ruthenium atoms; four terminal carbonyl ligands are associated with Ru(3), while Ru(l) and Ru(2) are each linked to three. In addition, Ru(l) and Ru(2) are bridged by a hydride ligand and by an μ-COMe ligand. (μ-H)Ru3(μ3-COMe)(CO)8(l,3-C6H8) (1) crystallizes in the triclinic space group P1 with a = 7.4916 (17) {\AA}, b = 8.7077 (19) {\AA}, c = 15.6023 (32) {\AA}, α = 89.995 (17)β = 97.832 (17γ = 98.991 (18)Z = 2. Data for 2θ(Mo Kα) = 4.0-50.0 were collected, and the structure was refined to RF = 2.3\% for all 3528 reflections. This molecule contains a triangular array of ruthenium atoms capped by a μ3-COMe ligand. There are three terminal carbonyl ligands each on Ru(l) and Ru(3), which are bridged by a hydride ligand; Ru(2) is linked to an)η4-l,3-cyclohexadiene ligand and bonded to two carbonyl ligands (which are weakly “semibridging” to Ru(l) and Ru(3)). A comparison of the structures of 1 and those of (μ-H)M3(μ-CX)(CO)10 (M = Fe, Ru, X = O-, NMe2, OMe; M = Os, X = H, NH-t-Bu), which have been determined previously, reveals that the coordination geometry adopted by the methylidyne moiety varies in a systematic manner with (i) the metal, (ii) the methylidyne substituent, and (iii) the other ligands of the cluster. These trends may have implications for the geometry adopted by alkylidyne fragments bound to metal surfaces.",

author = "Churchill, \{Melvyn Rowen\} and Beanan, \{Lawrence R.\} and Wasserman, \{Harvey J.\} and Clifford Bueno and Rahman, \{Zuraidah Abdul\} and Keister, \{Jerome B.\}",

year = "1983",

month = sep,

doi = "10.1021/om50003a019",

language = "English",

volume = "2",

pages = "1179--1186",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "9",

}

Churchill, MR, Beanan, LR, Wasserman, HJ, Bueno, C, Rahman, ZA & Keister, JB 1983, 'Synthesis of Cyclohexadiene Complexes of (Methylidyne)triruthenium Clusters. The Crystal Structure of (μ-H)Ru₃(μ₃-COCH₃)(CO)₈(1,3-C₆H₈) and a Redetermination of the Structure of (μ-H)Ru₃(μ-COCH₃)(CO)₁₀', Organometallics, vol. 2, no. 9, pp. 1179-1186. https://doi.org/10.1021/om50003a019

Synthesis of Cyclohexadiene Complexes of (Methylidyne)triruthenium Clusters. The Crystal Structure of (μ-H)Ru₃(μ₃-COCH₃)(CO)₈(1,3-C₆H₈) and a Redetermination of the Structure of (μ-H)Ru₃(μ-COCH₃)(CO)₁₀. / Churchill, Melvyn Rowen; Beanan, Lawrence R.; Wasserman, Harvey J. et al.
In: Organometallics, Vol. 2, No. 9, 09.1983, p. 1179-1186.

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

TY - JOUR

T1 - Synthesis of Cyclohexadiene Complexes of (Methylidyne)triruthenium Clusters. The Crystal Structure of (μ-H)Ru3(μ3-COCH3)(CO)8(1,3-C6H8) and a Redetermination of the Structure of (μ-H)Ru3(μ-COCH3)(CO)10

AU - Churchill, Melvyn Rowen

AU - Beanan, Lawrence R.

AU - Wasserman, Harvey J.

AU - Bueno, Clifford

AU - Rahman, Zuraidah Abdul

AU - Keister, Jerome B.

PY - 1983/9

Y1 - 1983/9

N2 - The complexes Gi-H)Ru3(μ3-CX)(CO)8(l,3-cyclohexadiene) (1, X = OMe; 2, X = Ph) are formed by reactions of the corresponding (μ-H)3Ru3(μ3-CX)(CO)9 with alkenes in the presence of excess 1,3-cyclohexadiene; 1 equiv of the hydrogenated alkene is also formed. The clusters 1 and 2 have been characterized spectroscopically, and the crystal structure of 1 has been determined by a complete three-dimensional X-ray crystallographic analysis. Because the structure of 1 differs significantly from that of the parent carbonyl (μ-H)Ru3(μ-COMe)(CO)10, a redetermination of the structure of the latter has also been performed. The complex (μ-H)Ru3(μ-COMe)(CO)10 crystallizes in the monoclinic space group P21/c with a = 7.9689 (17) Å,b = 17.0158 (42) Å, c = 14.1216 (30) Å, β = 104.082 (17), and Z = 4. Diffraction data were collected with a Syntex P21 diffractometer and refined to RF = 2.6% for all 2444 data with 2θ(Mo Kα) = 3.5-45.0. The molecule contains a triangular array of ruthenium atoms; four terminal carbonyl ligands are associated with Ru(3), while Ru(l) and Ru(2) are each linked to three. In addition, Ru(l) and Ru(2) are bridged by a hydride ligand and by an μ-COMe ligand. (μ-H)Ru3(μ3-COMe)(CO)8(l,3-C6H8) (1) crystallizes in the triclinic space group P1 with a = 7.4916 (17) Å, b = 8.7077 (19) Å, c = 15.6023 (32) Å, α = 89.995 (17)β = 97.832 (17γ = 98.991 (18)Z = 2. Data for 2θ(Mo Kα) = 4.0-50.0 were collected, and the structure was refined to RF = 2.3% for all 3528 reflections. This molecule contains a triangular array of ruthenium atoms capped by a μ3-COMe ligand. There are three terminal carbonyl ligands each on Ru(l) and Ru(3), which are bridged by a hydride ligand; Ru(2) is linked to an)η4-l,3-cyclohexadiene ligand and bonded to two carbonyl ligands (which are weakly “semibridging” to Ru(l) and Ru(3)). A comparison of the structures of 1 and those of (μ-H)M3(μ-CX)(CO)10 (M = Fe, Ru, X = O-, NMe2, OMe; M = Os, X = H, NH-t-Bu), which have been determined previously, reveals that the coordination geometry adopted by the methylidyne moiety varies in a systematic manner with (i) the metal, (ii) the methylidyne substituent, and (iii) the other ligands of the cluster. These trends may have implications for the geometry adopted by alkylidyne fragments bound to metal surfaces.

AB - The complexes Gi-H)Ru3(μ3-CX)(CO)8(l,3-cyclohexadiene) (1, X = OMe; 2, X = Ph) are formed by reactions of the corresponding (μ-H)3Ru3(μ3-CX)(CO)9 with alkenes in the presence of excess 1,3-cyclohexadiene; 1 equiv of the hydrogenated alkene is also formed. The clusters 1 and 2 have been characterized spectroscopically, and the crystal structure of 1 has been determined by a complete three-dimensional X-ray crystallographic analysis. Because the structure of 1 differs significantly from that of the parent carbonyl (μ-H)Ru3(μ-COMe)(CO)10, a redetermination of the structure of the latter has also been performed. The complex (μ-H)Ru3(μ-COMe)(CO)10 crystallizes in the monoclinic space group P21/c with a = 7.9689 (17) Å,b = 17.0158 (42) Å, c = 14.1216 (30) Å, β = 104.082 (17), and Z = 4. Diffraction data were collected with a Syntex P21 diffractometer and refined to RF = 2.6% for all 2444 data with 2θ(Mo Kα) = 3.5-45.0. The molecule contains a triangular array of ruthenium atoms; four terminal carbonyl ligands are associated with Ru(3), while Ru(l) and Ru(2) are each linked to three. In addition, Ru(l) and Ru(2) are bridged by a hydride ligand and by an μ-COMe ligand. (μ-H)Ru3(μ3-COMe)(CO)8(l,3-C6H8) (1) crystallizes in the triclinic space group P1 with a = 7.4916 (17) Å, b = 8.7077 (19) Å, c = 15.6023 (32) Å, α = 89.995 (17)β = 97.832 (17γ = 98.991 (18)Z = 2. Data for 2θ(Mo Kα) = 4.0-50.0 were collected, and the structure was refined to RF = 2.3% for all 3528 reflections. This molecule contains a triangular array of ruthenium atoms capped by a μ3-COMe ligand. There are three terminal carbonyl ligands each on Ru(l) and Ru(3), which are bridged by a hydride ligand; Ru(2) is linked to an)η4-l,3-cyclohexadiene ligand and bonded to two carbonyl ligands (which are weakly “semibridging” to Ru(l) and Ru(3)). A comparison of the structures of 1 and those of (μ-H)M3(μ-CX)(CO)10 (M = Fe, Ru, X = O-, NMe2, OMe; M = Os, X = H, NH-t-Bu), which have been determined previously, reveals that the coordination geometry adopted by the methylidyne moiety varies in a systematic manner with (i) the metal, (ii) the methylidyne substituent, and (iii) the other ligands of the cluster. These trends may have implications for the geometry adopted by alkylidyne fragments bound to metal surfaces.

UR - https://www.scopus.com/pages/publications/0011023030

U2 - 10.1021/om50003a019

DO - 10.1021/om50003a019

M3 - Article

SN - 0276-7333

VL - 2

SP - 1179

EP - 1186

JO - Organometallics

JF - Organometallics

IS - 9