Preparation of [Os3(CO)11]2− and its reactions with OS3(CO)12; structures of [Et4N][HOs3(CO)11] and H2 OS4(CO

doi:10.1016/0022-328X(93)83250-Y

Journal of Organometallic Chemistry

Volume 454, Issues 1–2, 27 July 1993, Pages 263-271

https://doi.org/10.1016/0022-328X(93)83250-Y Get rights and content

Abstract

The dianion [Os₃(CO)₁₁]²⁻ has been prepared by stoichiometric reduction of Os₃(CO)₁₂ with potassium-benzophenone ketyl. Infrared of [Et₄N][HOs₃(CO)₁₁] was determined from a single crystal X-ray analysis. The anion structure consists of an Os₃ triangle. One Os atom for 3558 independent reflections with I ⩾ 3σ(I). H₂Os₄(CO)₁₃ was prepared by the reaction of K₂[Os₃(CO)₁₁] with Os( These basal Os atoms are bridged by two single ii-H atoms. Crystal data for H₂Os₄(CO)₁₃: space group P $1$ , a = 9.129(4) Å,

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Substitution derivatives of the heteronuclear cluster RuOs<inf>3</inf>(μ-H)<inf>2</inf>(CO)<inf>13</inf>: Disubstituted group 15 derivatives
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The structures in the solid state and solution state of tertiary group 15 ligand disubstituted derivatives of the heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ are examined. Four structural types have been characterised crystallographically, including one in which both phosphine ligands were substituted at the unique ruthenium vertex. In solution, there are many more isomers present, most of which are rapidly interconverting via hydride migrations. Substitution appears to be directed electronically to the ruthenium vertex, although steric hindrance appears to drive subsequent isomerisation via migration of the second group 15 ligand.
Remarkably stable radical anions derived from clusters [HOs<inf>3</inf>(CO)<inf>9</inf>(L)], L=ortho-metallated α-diimine: A spectro-electrochemical study and theoretical rationalization<sup>1</sup>
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Reduction of the cluster [Os₃(CO)₁₀(ⁱPr-PyCa)], ⁱPr–PyCa=σ-N,σ-N′-pyridine-2-carbaldehyde-N-isopropyl-imine, (1) follows an ECEC sequence. The initial one-electron reduction step produces the radical anion 1⁻ which was found stable on a subsecond time scale at low temperatures. At room temperature an open-structure radical anionic transient 1a⁻ is formed which instantaneously reduces to 1a²⁻. Subsequent attack of the latter species at yet nonreduced 1 yields an Os–Os bonded cluster dimer [1a–1a]²⁻. In contrast to the reactivity of 1⁻, the radical anions of the clusters [HOs₃(CO)₉(C₅H₃N-2-C(H)N–ⁱPr)] (2), [HOs₃(CO)₉(6-CH₂–C₅H₃N-2-C(H)N–ⁱPr)] (3), containing the ortho-metallated ligands o-ⁱPr–PyCa{6-X} (X=H, Me}, are substantially more stable. At room temperature in THF, 2⁻ and 3⁻ slowly disproportionate to moderately stable dianionic species 2b and 3c. IR and ¹H-NMR spectra of 2b have revealed the presence of bridging CO and terminal hydride ligands, and the dominant localization of the negative charge on the metallic core. The structure of 3c is probably similar. The latter dianions were also obtained by direct one-electron reduction of 2⁻ and 3⁻, respectively. Both radical anions are inherently stable at T=253 K. According to extended Hückel molecular orbital calculations on models of the parent clusters 1–3, the higher stability of 2⁻ and 3⁻ relative to that of 1⁻ has its origin in larger localization of the odd electron at the lowest π*-orbital of the ortho-metallated ligands compared to the σN,σN′-chelated ⁱPr–PyCa ligand, and in higher cluster-diimine binding energies of 2 and 3 which drop due the one-electron reduction less than calculated for the couple 1/1⁻. IR and ¹H-NMR spectra have revealed that 2,3-dipyrid-2′-ylbenzoquinoxaline (dpb) coordinates to the Os₃ core as an ortho-metallated ligand, forming [HOs₃(CO)₉(dpb-14-yl)] (4), in contrast to shorter 2,3-dipyrid-2′-ylpyrazine (dpp). The corresponding radical anion 4⁻ is inherently stable already at room temperature, mainly due to the large π-acceptor capacity of the ortho-metallated dpb ligand.
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Preparation of [Os3(CO)11]2− and its reactions with OS3(CO)12; structures of [Et4N][HOs3(CO)11] and H2 OS4(CO

Abstract

J. Organomet. Chem.

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

Organometallics

Organometallics

Inorg. Chem.

J. Am. Chem. Soc.

J. Chem. Soc., Dalton Trans.

J. Chem. Soc. (A)

J. Chem. Soc., Dalton Trans.

J. Chem. Soc. Dalton Trans.

J. Chem. Soc., Chem. Commun.

J. Chem. Soc., Chem. Commun.

J. Organomet. Chem.

J. Chem. Soc., Dalton Trans.

Preparation of [Os₃(CO)₁₁]²⁻ and its reactions with OS₃(CO)₁₂; structures of [Et₄N][HOs₃(CO)₁₁] and H₂ OS₄(CO