Synthesis and Interconversions of Several Tri- and Tetranuclear Ruthenium Isocyanato Carbonyl Clusters. Crystal and Molecular Structure of H3Ru4(NCO)(CO)12

Douglas E. Fjare; James A. Jensen; Wayne L. Gladfelter

doi:10.1021/ic00154a017

Synthesis and Interconversions of Several Tri- and Tetranuclear Ruthenium Isocyanato Carbonyl Clusters. Crystal and Molecular Structure of H₃Ru₄(NCO)(CO)₁₂

Douglas E. Fjare, James A. Jensen, Wayne L. Gladfelter

Chemistry (Twin Cities)

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Abstract

The reaction of Ru₃(CO)₁₂ with PPN(N₃) was found to lead through several intermediates to PPN[Ru₄(NCO)(CO)₁₃]. The structure of this product is proposed to be analogous to [Ru₄Cl(CO)₁₃]- with the μ-NCO replacing the chloride. Spectroscopic characterization of the intermediates suggests that their formulations are [Ru₃(NCO)(CO)₁₁]- and [Ru₃-(NCO)(CO)₁₀]-. Protonation of the initial reaction solution containing these trimers allows the isolation of HRu₃(NCO)(CO)₁₀ in low yield. The tetranuclear cluster reacts with CO at room temperature to give [Ru₃(NCO)(CO)₁₁]-, and it reacts with H₂ under the same conditions to give [H₂Ru₄(NCO)(CO)₁₂]-. This anion reacts with CF₃SO₃H to give H₃Ru₄(NCO)(CO)₁₂, which was characterized by a single-crystal X-ray crystallographic study [P2₁/n space group; a = 9.836 (2), b = 22.063 (5), c = 10.056 (2) Å; β = 97.93 (1)°; V= 2161 (1) Å³; Z = 4; final R = 0.024; final R_w = 0.028]. The structure contains a butterfly arrangement of ruthenium tricarbonyl groups with the isocyanate bridging the open edge. The hydrogen atoms were located and refined.

Original language	English (US)
Pages (from-to)	1774-1780
Number of pages	7
Journal	Inorganic Chemistry
Volume	22
Issue number	12
DOIs	https://doi.org/10.1021/ic00154a017
State	Published - Jun 1983

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@article{dc9c63dd02f34a0eb5468dd73e6dcff2,

title = "Synthesis and Interconversions of Several Tri- and Tetranuclear Ruthenium Isocyanato Carbonyl Clusters. Crystal and Molecular Structure of H3Ru4(NCO)(CO)12",

abstract = "The reaction of Ru3(CO)12 with PPN(N3) was found to lead through several intermediates to PPN[Ru4(NCO)(CO)13]. The structure of this product is proposed to be analogous to [Ru4Cl(CO)13]- with the μ-NCO replacing the chloride. Spectroscopic characterization of the intermediates suggests that their formulations are [Ru3(NCO)(CO)11]- and [Ru3-(NCO)(CO)10]-. Protonation of the initial reaction solution containing these trimers allows the isolation of HRu3(NCO)(CO)10 in low yield. The tetranuclear cluster reacts with CO at room temperature to give [Ru3(NCO)(CO)11]-, and it reacts with H2 under the same conditions to give [H2Ru4(NCO)(CO)12]-. This anion reacts with CF3SO3H to give H3Ru4(NCO)(CO)12, which was characterized by a single-crystal X-ray crystallographic study [P21/n space group; a = 9.836 (2), b = 22.063 (5), c = 10.056 (2) {\AA}; β = 97.93 (1)°; V= 2161 (1) {\AA}3; Z = 4; final R = 0.024; final Rw = 0.028]. The structure contains a butterfly arrangement of ruthenium tricarbonyl groups with the isocyanate bridging the open edge. The hydrogen atoms were located and refined.",

author = "Fjare, {Douglas E.} and Jensen, {James A.} and Gladfelter, {Wayne L.}",

year = "1983",

month = jun,

doi = "10.1021/ic00154a017",

language = "English (US)",

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pages = "1774--1780",

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T1 - Synthesis and Interconversions of Several Tri- and Tetranuclear Ruthenium Isocyanato Carbonyl Clusters. Crystal and Molecular Structure of H3Ru4(NCO)(CO)12

AU - Fjare, Douglas E.

AU - Jensen, James A.

AU - Gladfelter, Wayne L.

PY - 1983/6

Y1 - 1983/6

N2 - The reaction of Ru3(CO)12 with PPN(N3) was found to lead through several intermediates to PPN[Ru4(NCO)(CO)13]. The structure of this product is proposed to be analogous to [Ru4Cl(CO)13]- with the μ-NCO replacing the chloride. Spectroscopic characterization of the intermediates suggests that their formulations are [Ru3(NCO)(CO)11]- and [Ru3-(NCO)(CO)10]-. Protonation of the initial reaction solution containing these trimers allows the isolation of HRu3(NCO)(CO)10 in low yield. The tetranuclear cluster reacts with CO at room temperature to give [Ru3(NCO)(CO)11]-, and it reacts with H2 under the same conditions to give [H2Ru4(NCO)(CO)12]-. This anion reacts with CF3SO3H to give H3Ru4(NCO)(CO)12, which was characterized by a single-crystal X-ray crystallographic study [P21/n space group; a = 9.836 (2), b = 22.063 (5), c = 10.056 (2) Å; β = 97.93 (1)°; V= 2161 (1) Å3; Z = 4; final R = 0.024; final Rw = 0.028]. The structure contains a butterfly arrangement of ruthenium tricarbonyl groups with the isocyanate bridging the open edge. The hydrogen atoms were located and refined.

AB - The reaction of Ru3(CO)12 with PPN(N3) was found to lead through several intermediates to PPN[Ru4(NCO)(CO)13]. The structure of this product is proposed to be analogous to [Ru4Cl(CO)13]- with the μ-NCO replacing the chloride. Spectroscopic characterization of the intermediates suggests that their formulations are [Ru3(NCO)(CO)11]- and [Ru3-(NCO)(CO)10]-. Protonation of the initial reaction solution containing these trimers allows the isolation of HRu3(NCO)(CO)10 in low yield. The tetranuclear cluster reacts with CO at room temperature to give [Ru3(NCO)(CO)11]-, and it reacts with H2 under the same conditions to give [H2Ru4(NCO)(CO)12]-. This anion reacts with CF3SO3H to give H3Ru4(NCO)(CO)12, which was characterized by a single-crystal X-ray crystallographic study [P21/n space group; a = 9.836 (2), b = 22.063 (5), c = 10.056 (2) Å; β = 97.93 (1)°; V= 2161 (1) Å3; Z = 4; final R = 0.024; final Rw = 0.028]. The structure contains a butterfly arrangement of ruthenium tricarbonyl groups with the isocyanate bridging the open edge. The hydrogen atoms were located and refined.

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Synthesis and Interconversions of Several Tri- and Tetranuclear Ruthenium Isocyanato Carbonyl Clusters. Crystal and Molecular Structure of H₃Ru₄(NCO)(CO)₁₂

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