47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H2Ru3(RC2R')(CO)6(PPh3)3 and Crystal Structures of (μ-H)2Ru3(μ3-η2-EtCCEt)(CO)7(PPh3)2 and (μ-H)2Ru3(μ3-η2-EtCCEt)(CO)6(PPh3)3·3CH2Cl2

Witold Paw; Charles H. Lake; Melvyn Rowen Churchill; Jerome B. Keister

doi:10.1021/om00008a026

47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H₂Ru₃(RC₂R')(CO)₆(PPh₃)₃ and Crystal Structures of (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₇(PPh₃)₂ and (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₆(PPh₃)₃·3CH₂Cl₂

Witold Paw
, Charles H. Lake
, Melvyn Rowen Churchill
, Jerome B. Keister

Chemistry

SUNY Buffalo

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

12 Scopus citations

Abstract

Electrochemical and chemical oxidations of 48-electron clusters (μ-H)2ru₃(RCCR')(CO)₆(PPh₃)₃(RCCR' = EtCCEt, HCCOEt, PhCCPh) give unstable radical cations. The radical cation derived from (μ-H)₂Ru₃(EtCCEt)(CO)₆(PPh₃)₃ decomposes in the presence of halide sources primarily by disproportionation to [(μ-H)₂Ru₃(μ-X)(EtCCEt)(CO)₆(PPh₃)₃]⁺(X = F, Cl). Electrophilic additions using Cl₂,I₂, and CF₃CO₂H give the analogous [(μ-H)₂Ru3(μ-X)(EtCCEt)(CO)₆(PPh₃)₃]⁺ (X = Cl, I, H). Although the 48-/46-electron couple [Fe₃(RCCR)(CO)₉]^2-/Fe₃(RCCR)(CO)₉ is well-documented, and the 46-electron cluster [H₂Ru₃(HC₂CMe₃)(CO)_9-n(PPh₃)_n]²⁺ has been reported to be stable, there is no evidence for formation of 46-electron [H₂Ru₃(RCCR')(CO)₆(PPh₃)₃]²⁺ by two-electron oxidation of (μ-H)₂Ru₃(RCCR')(CO)₆(PPh₃)₃. Two crystal structures are reported. For the diphosphine derivative (μ-H)2ru3(EtCCEt)(CO)₇(PPh₃)₂, the single Ru(1)-Ru(3) bond length is 2.757(2) Å while the hydrido-bridged distances are Ru(1)-Ru(2) = 2.889(2) Å and Ru(2)-Ru(3) = 2.993(2) Å. The EtCCEt ligand is σ-bonded to Ru(2) and Ru(3) (Ru(2)-C(2) = 2.118(8) Å and Ru(3)-C(1) = 2.123(8) Å) and π-bonded to Ru(1) (Ru(1)-C(1) = 2.338(7) Å and Ru(1)-C(2) = 2.295(9) Å). One PPh₃ ligand occupies an equatorial site on Ru(1); the second occupies an axial site on Ru(2), trans to the Ru(2)-alkyne σ-bond. The single Ru(1)-Ru(3) bond length for (μ-H)2ru₃(EtCCEt)(CO)₆(PPh₃)₃·3CH₂Cl₂ is 2.744(1) Å while the hydrido-bridged distances are Ru-(1)-Ru(2) = 2.891(1) Å and Ru(2)-Ru(3) = 3.077(1) Å. The EtCCEt ligand is bonded in the same 2σ,π-manner as for the previous structure. Two PPh₃ ligands occupy those same two sites as in the diphosphine complex (equatorial on Ru(1), axial on Ru(2)), while the third occupies a close-to-equatorial site on Ru(3). Hydride ligands were located and refined in each structural study.

Original language	English
Pages (from-to)	3768-3782
Number of pages	15
Journal	Organometallics
Volume	14
Issue number	8
DOIs	https://doi.org/10.1021/om00008a026
State	Published - Aug 1995

Access to Document

10.1021/om00008a026

Fingerprint

Dive into the research topics of '47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H₂Ru₃(RC₂R')(CO)₆(PPh₃)₃ and Crystal Structures of (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₇(PPh₃)₂ and (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₆(PPh₃)₃·3CH₂Cl₂'. Together they form a unique fingerprint.

Cite this

Paw, W., Lake, C. H., Churchill, M. R., & Keister, J. B. (1995). 47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H₂Ru₃(RC₂R')(CO)₆(PPh₃)₃ and Crystal Structures of (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₇(PPh₃)₂ and (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₆(PPh₃)₃·3CH₂Cl₂. Organometallics, 14(8), 3768-3782. https://doi.org/10.1021/om00008a026

Paw, Witold ; Lake, Charles H. ; Churchill, Melvyn Rowen et al. / 47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H₂Ru₃(RC₂R')(CO)₆(PPh₃)₃ and Crystal Structures of (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₇(PPh₃)₂ and (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₆(PPh₃)₃·3CH₂Cl₂. In: Organometallics. 1995 ; Vol. 14, No. 8. pp. 3768-3782.

@article{adb41044b24f4f2ebf32e003ac8bed55,

title = "47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H2Ru3(RC2R')(CO)6(PPh3)3 and Crystal Structures of (μ-H)2Ru3(μ3-η2-EtCCEt)(CO)7(PPh3)2 and (μ-H)2Ru3(μ3-η2-EtCCEt)(CO)6(PPh3)3·3CH2Cl2",

abstract = "Electrochemical and chemical oxidations of 48-electron clusters (μ-H)2ru3(RCCR')(CO)6(PPh3)3(RCCR' = EtCCEt, HCCOEt, PhCCPh) give unstable radical cations. The radical cation derived from (μ-H)2Ru3(EtCCEt)(CO)6(PPh3)3 decomposes in the presence of halide sources primarily by disproportionation to [(μ-H)2Ru3(μ-X)(EtCCEt)(CO)6(PPh3)3]+(X = F, Cl). Electrophilic additions using Cl2,I2, and CF3CO2H give the analogous [(μ-H)2Ru3(μ-X)(EtCCEt)(CO)6(PPh3)3]+ (X = Cl, I, H). Although the 48-/46-electron couple [Fe3(RCCR)(CO)9]2-/Fe3(RCCR)(CO)9 is well-documented, and the 46-electron cluster [H2Ru3(HC2CMe3)(CO)9-n(PPh3)n]2+ has been reported to be stable, there is no evidence for formation of 46-electron [H2Ru3(RCCR')(CO)6(PPh3)3]2+ by two-electron oxidation of (μ-H)2Ru3(RCCR')(CO)6(PPh3)3. Two crystal structures are reported. For the diphosphine derivative (μ-H)2ru3(EtCCEt)(CO)7(PPh3)2, the single Ru(1)-Ru(3) bond length is 2.757(2) {\AA} while the hydrido-bridged distances are Ru(1)-Ru(2) = 2.889(2) {\AA} and Ru(2)-Ru(3) = 2.993(2) {\AA}. The EtCCEt ligand is σ-bonded to Ru(2) and Ru(3) (Ru(2)-C(2) = 2.118(8) {\AA} and Ru(3)-C(1) = 2.123(8) {\AA}) and π-bonded to Ru(1) (Ru(1)-C(1) = 2.338(7) {\AA} and Ru(1)-C(2) = 2.295(9) {\AA}). One PPh3 ligand occupies an equatorial site on Ru(1); the second occupies an axial site on Ru(2), trans to the Ru(2)-alkyne σ-bond. The single Ru(1)-Ru(3) bond length for (μ-H)2ru3(EtCCEt)(CO)6(PPh3)3·3CH2Cl2 is 2.744(1) {\AA} while the hydrido-bridged distances are Ru-(1)-Ru(2) = 2.891(1) {\AA} and Ru(2)-Ru(3) = 3.077(1) {\AA}. The EtCCEt ligand is bonded in the same 2σ,π-manner as for the previous structure. Two PPh3 ligands occupy those same two sites as in the diphosphine complex (equatorial on Ru(1), axial on Ru(2)), while the third occupies a close-to-equatorial site on Ru(3). Hydride ligands were located and refined in each structural study.",

author = "Witold Paw and Lake, \{Charles H.\} and Churchill, \{Melvyn Rowen\} and Keister, \{Jerome B.\}",

year = "1995",

month = aug,

doi = "10.1021/om00008a026",

language = "English",

volume = "14",

pages = "3768--3782",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "8",

}

Paw, W, Lake, CH, Churchill, MR & Keister, JB 1995, '47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H₂Ru₃(RC₂R')(CO)₆(PPh₃)₃ and Crystal Structures of (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₇(PPh₃)₂ and (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₆(PPh₃)₃·3CH₂Cl₂', Organometallics, vol. 14, no. 8, pp. 3768-3782. https://doi.org/10.1021/om00008a026

47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H₂Ru₃(RC₂R')(CO)₆(PPh₃)₃ and Crystal Structures of (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₇(PPh₃)₂ and (μ-H)₂Ru₃(μ₃-η²-EtCCEt)(CO)₆(PPh₃)₃·3CH₂Cl₂. / Paw, Witold; Lake, Charles H.; Churchill, Melvyn Rowen et al.
In: Organometallics, Vol. 14, No. 8, 08.1995, p. 3768-3782.

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

TY - JOUR

T1 - 47-Electron Organometallic Clusters. Synthesis, Characterization, and Reactivity toward Electrophiles/ Oxidants of H2Ru3(RC2R')(CO)6(PPh3)3 and Crystal Structures of (μ-H)2Ru3(μ3-η2-EtCCEt)(CO)7(PPh3)2 and (μ-H)2Ru3(μ3-η2-EtCCEt)(CO)6(PPh3)3·3CH2Cl2

AU - Paw, Witold

AU - Lake, Charles H.

AU - Churchill, Melvyn Rowen

AU - Keister, Jerome B.

PY - 1995/8

Y1 - 1995/8

N2 - Electrochemical and chemical oxidations of 48-electron clusters (μ-H)2ru3(RCCR')(CO)6(PPh3)3(RCCR' = EtCCEt, HCCOEt, PhCCPh) give unstable radical cations. The radical cation derived from (μ-H)2Ru3(EtCCEt)(CO)6(PPh3)3 decomposes in the presence of halide sources primarily by disproportionation to [(μ-H)2Ru3(μ-X)(EtCCEt)(CO)6(PPh3)3]+(X = F, Cl). Electrophilic additions using Cl2,I2, and CF3CO2H give the analogous [(μ-H)2Ru3(μ-X)(EtCCEt)(CO)6(PPh3)3]+ (X = Cl, I, H). Although the 48-/46-electron couple [Fe3(RCCR)(CO)9]2-/Fe3(RCCR)(CO)9 is well-documented, and the 46-electron cluster [H2Ru3(HC2CMe3)(CO)9-n(PPh3)n]2+ has been reported to be stable, there is no evidence for formation of 46-electron [H2Ru3(RCCR')(CO)6(PPh3)3]2+ by two-electron oxidation of (μ-H)2Ru3(RCCR')(CO)6(PPh3)3. Two crystal structures are reported. For the diphosphine derivative (μ-H)2ru3(EtCCEt)(CO)7(PPh3)2, the single Ru(1)-Ru(3) bond length is 2.757(2) Å while the hydrido-bridged distances are Ru(1)-Ru(2) = 2.889(2) Å and Ru(2)-Ru(3) = 2.993(2) Å. The EtCCEt ligand is σ-bonded to Ru(2) and Ru(3) (Ru(2)-C(2) = 2.118(8) Å and Ru(3)-C(1) = 2.123(8) Å) and π-bonded to Ru(1) (Ru(1)-C(1) = 2.338(7) Å and Ru(1)-C(2) = 2.295(9) Å). One PPh3 ligand occupies an equatorial site on Ru(1); the second occupies an axial site on Ru(2), trans to the Ru(2)-alkyne σ-bond. The single Ru(1)-Ru(3) bond length for (μ-H)2ru3(EtCCEt)(CO)6(PPh3)3·3CH2Cl2 is 2.744(1) Å while the hydrido-bridged distances are Ru-(1)-Ru(2) = 2.891(1) Å and Ru(2)-Ru(3) = 3.077(1) Å. The EtCCEt ligand is bonded in the same 2σ,π-manner as for the previous structure. Two PPh3 ligands occupy those same two sites as in the diphosphine complex (equatorial on Ru(1), axial on Ru(2)), while the third occupies a close-to-equatorial site on Ru(3). Hydride ligands were located and refined in each structural study.

AB - Electrochemical and chemical oxidations of 48-electron clusters (μ-H)2ru3(RCCR')(CO)6(PPh3)3(RCCR' = EtCCEt, HCCOEt, PhCCPh) give unstable radical cations. The radical cation derived from (μ-H)2Ru3(EtCCEt)(CO)6(PPh3)3 decomposes in the presence of halide sources primarily by disproportionation to [(μ-H)2Ru3(μ-X)(EtCCEt)(CO)6(PPh3)3]+(X = F, Cl). Electrophilic additions using Cl2,I2, and CF3CO2H give the analogous [(μ-H)2Ru3(μ-X)(EtCCEt)(CO)6(PPh3)3]+ (X = Cl, I, H). Although the 48-/46-electron couple [Fe3(RCCR)(CO)9]2-/Fe3(RCCR)(CO)9 is well-documented, and the 46-electron cluster [H2Ru3(HC2CMe3)(CO)9-n(PPh3)n]2+ has been reported to be stable, there is no evidence for formation of 46-electron [H2Ru3(RCCR')(CO)6(PPh3)3]2+ by two-electron oxidation of (μ-H)2Ru3(RCCR')(CO)6(PPh3)3. Two crystal structures are reported. For the diphosphine derivative (μ-H)2ru3(EtCCEt)(CO)7(PPh3)2, the single Ru(1)-Ru(3) bond length is 2.757(2) Å while the hydrido-bridged distances are Ru(1)-Ru(2) = 2.889(2) Å and Ru(2)-Ru(3) = 2.993(2) Å. The EtCCEt ligand is σ-bonded to Ru(2) and Ru(3) (Ru(2)-C(2) = 2.118(8) Å and Ru(3)-C(1) = 2.123(8) Å) and π-bonded to Ru(1) (Ru(1)-C(1) = 2.338(7) Å and Ru(1)-C(2) = 2.295(9) Å). One PPh3 ligand occupies an equatorial site on Ru(1); the second occupies an axial site on Ru(2), trans to the Ru(2)-alkyne σ-bond. The single Ru(1)-Ru(3) bond length for (μ-H)2ru3(EtCCEt)(CO)6(PPh3)3·3CH2Cl2 is 2.744(1) Å while the hydrido-bridged distances are Ru-(1)-Ru(2) = 2.891(1) Å and Ru(2)-Ru(3) = 3.077(1) Å. The EtCCEt ligand is bonded in the same 2σ,π-manner as for the previous structure. Two PPh3 ligands occupy those same two sites as in the diphosphine complex (equatorial on Ru(1), axial on Ru(2)), while the third occupies a close-to-equatorial site on Ru(3). Hydride ligands were located and refined in each structural study.

UR - https://www.scopus.com/pages/publications/0010703550

U2 - 10.1021/om00008a026

DO - 10.1021/om00008a026

M3 - Article

AN - SCOPUS:0010703550

SN - 0276-7333

VL - 14

SP - 3768

EP - 3782

JO - Organometallics

JF - Organometallics

IS - 8