Decacarbonylnitrosyltriosmate(3 Os-Os)(1-): Structural Analysis and Fluxional Properties

Brian F.G. Johnson; Jack Lewis; Julian M. Mace; Paul R. Raithby; Robert E. Stevens; Wayne L. Gladfelter

doi:10.1021/ic00179a029

Decacarbonylnitrosyltriosmate(3 Os-Os)(1-): Structural Analysis and Fluxional Properties

Brian F.G. Johnson, Jack Lewis, Julian M. Mace, Paul R. Raithby, Robert E. Stevens, Wayne L. Gladfelter

Chemistry (Twin Cities)

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

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Abstract

The crystal and molecular structure of PPN[Os₃(CO)₁₀(NO)] (PPN = [P(C₆H₅)₃]₂N⁺) has been determined by a single-crystal X-ray analysis. The compound crystallizes in the monoclinic crystal system in space group P2¹/c with a = 16.848 (2) Å, b = 17.015 (2) Å, c = 17.740 (2) Å, β = 107.25 (1)^°, and ρ(calcd) = 1.94 g cm^-3 for Z = 4 with molecular weight 1419.26. Diffraction data were recorded on a Stoe-Siemens diffractometer, and the structure was refined to R = 0.045 for 6261 observed diffractometer data. The three osmium atoms lie at the vertices of an isoceles triangle with the nitrosyl ligand bridging the shorter Os-Os edge. The arrangement of the three terminal carbonyl groups bound to each of the metal atoms bridged by the nitrosyl ligand is different from that in the saturated HOs₃(CO)₁₀(X) clusters, and the bridged Os-Os bond length of 2.751 (1) Å is shorter than that found in any of these related neutral species. This difference between the two types of systems may be attributed to the absence of a bridging hydride in the anion. The lack of this hydride is also proposed to be responsible for the lower activation barrier for CO scrambling observed in [Os₃(CO)₁₀(NO)]^-.

Original language	English (US)
Pages (from-to)	1600-1603
Number of pages	4
Journal	Inorganic Chemistry
Volume	23
Issue number	11
DOIs	https://doi.org/10.1021/ic00179a029
State	Published - Mar 1984

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title = "Decacarbonylnitrosyltriosmate(3 Os-Os)(1-): Structural Analysis and Fluxional Properties",

abstract = "The crystal and molecular structure of PPN[Os3(CO)10(NO)] (PPN = [P(C6H5)3]2N+) has been determined by a single-crystal X-ray analysis. The compound crystallizes in the monoclinic crystal system in space group P21/c with a = 16.848 (2) {\AA}, b = 17.015 (2) {\AA}, c = 17.740 (2) {\AA}, β = 107.25 (1)°, and ρ(calcd) = 1.94 g cm-3 for Z = 4 with molecular weight 1419.26. Diffraction data were recorded on a Stoe-Siemens diffractometer, and the structure was refined to R = 0.045 for 6261 observed diffractometer data. The three osmium atoms lie at the vertices of an isoceles triangle with the nitrosyl ligand bridging the shorter Os-Os edge. The arrangement of the three terminal carbonyl groups bound to each of the metal atoms bridged by the nitrosyl ligand is different from that in the saturated HOs3(CO)10(X) clusters, and the bridged Os-Os bond length of 2.751 (1) {\AA} is shorter than that found in any of these related neutral species. This difference between the two types of systems may be attributed to the absence of a bridging hydride in the anion. The lack of this hydride is also proposed to be responsible for the lower activation barrier for CO scrambling observed in [Os3(CO)10(NO)]-.",

author = "Johnson, {Brian F.G.} and Jack Lewis and Mace, {Julian M.} and Raithby, {Paul R.} and Stevens, {Robert E.} and Gladfelter, {Wayne L.}",

year = "1984",

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doi = "10.1021/ic00179a029",

language = "English (US)",

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T1 - Decacarbonylnitrosyltriosmate(3 Os-Os)(1-)

T2 - Structural Analysis and Fluxional Properties

AU - Johnson, Brian F.G.

AU - Lewis, Jack

AU - Mace, Julian M.

AU - Raithby, Paul R.

AU - Stevens, Robert E.

AU - Gladfelter, Wayne L.

PY - 1984/3

Y1 - 1984/3

N2 - The crystal and molecular structure of PPN[Os3(CO)10(NO)] (PPN = [P(C6H5)3]2N+) has been determined by a single-crystal X-ray analysis. The compound crystallizes in the monoclinic crystal system in space group P21/c with a = 16.848 (2) Å, b = 17.015 (2) Å, c = 17.740 (2) Å, β = 107.25 (1)°, and ρ(calcd) = 1.94 g cm-3 for Z = 4 with molecular weight 1419.26. Diffraction data were recorded on a Stoe-Siemens diffractometer, and the structure was refined to R = 0.045 for 6261 observed diffractometer data. The three osmium atoms lie at the vertices of an isoceles triangle with the nitrosyl ligand bridging the shorter Os-Os edge. The arrangement of the three terminal carbonyl groups bound to each of the metal atoms bridged by the nitrosyl ligand is different from that in the saturated HOs3(CO)10(X) clusters, and the bridged Os-Os bond length of 2.751 (1) Å is shorter than that found in any of these related neutral species. This difference between the two types of systems may be attributed to the absence of a bridging hydride in the anion. The lack of this hydride is also proposed to be responsible for the lower activation barrier for CO scrambling observed in [Os3(CO)10(NO)]-.

AB - The crystal and molecular structure of PPN[Os3(CO)10(NO)] (PPN = [P(C6H5)3]2N+) has been determined by a single-crystal X-ray analysis. The compound crystallizes in the monoclinic crystal system in space group P21/c with a = 16.848 (2) Å, b = 17.015 (2) Å, c = 17.740 (2) Å, β = 107.25 (1)°, and ρ(calcd) = 1.94 g cm-3 for Z = 4 with molecular weight 1419.26. Diffraction data were recorded on a Stoe-Siemens diffractometer, and the structure was refined to R = 0.045 for 6261 observed diffractometer data. The three osmium atoms lie at the vertices of an isoceles triangle with the nitrosyl ligand bridging the shorter Os-Os edge. The arrangement of the three terminal carbonyl groups bound to each of the metal atoms bridged by the nitrosyl ligand is different from that in the saturated HOs3(CO)10(X) clusters, and the bridged Os-Os bond length of 2.751 (1) Å is shorter than that found in any of these related neutral species. This difference between the two types of systems may be attributed to the absence of a bridging hydride in the anion. The lack of this hydride is also proposed to be responsible for the lower activation barrier for CO scrambling observed in [Os3(CO)10(NO)]-.

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Decacarbonylnitrosyltriosmate(3 Os-Os)(1-): Structural Analysis and Fluxional Properties

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