Ligand substitution of FeRu2(CO)12 and Fe2Ru(CO)12 with tertiary phosphines and phosphites

doi:10.1016/0022-328X(84)80139-4

Journal of Organometallic Chemistry

Volume 266, Issue 3, 8 May 1984, Pages 269-283

https://doi.org/10.1016/0022-328X(84)80139-4 Get rights and content

Abstract

Ligand substitution of the mixed-metal clusters FeRu₂(CO)₁₂ and Fe₂Ru(CO)₁₂ with triphenylphosphine and trimethylphosphite has been studied. Mono- and di-substituted derivatives have been synthesized and characterized structurally. The following crystal and molecular structures are reported: Fe₂Ru(CO)₁₁PPh₃: triclinic, space group P $1$ , a 9.203(2), b 11.903(3), c 15.117(4) Å, α 81.54(2), β 87.28(2), γ 66.72(2)°, Z = 2; Fe₂Ru(CO)₁₁P(OMe)₃: orthorhombic, space group Pna2₁, a 17.220(5), b 14.572(4), c 8.708(6) Å, Z = 4, FeRu₂(CO)₁₁PPh₃: monoclinic, space group P2₁/n, a 11.435(3), b 16.034(5), c 16.642(4) Å, β 93.35(2)°, Z = 4; FeRu₂(CO)₁₀(PPh₃)₂: orthorhombic, space group Pccm, a 14.854(4), b 17.180(7), c 16.786(12) Å, Z = 4.

Ligand substitution is found to occur preferentially at the ruthenium centers of the FeRu₂ and Fe₂Ru clusters. Monosubstitution causes expansion of both of the clusters while the overall geometry is practically unchanged. Disubstitution of FeRu₂(CO)₁₂ causes contraction of the cluster and leads to a formation of carbonyl bridges. The structural trends have been interpreted in terms of electronic and packing effects of ligand substitution. The X-ray structures of Fe₂Ru(CO)₁₂ and FeRu₂(CO)₁₂ are not known; the ligand substitution studies indicate that Fe₂Ru(CO)₁₂ has the same structure as Fe₃(CO)₁₂, and that FeRu₃(CO)₁₂ does not have a Ru₃(CO)₁₂ structure as postulated previously from the IR studies.

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Preparation of the new heteronuclear α-diimine complexes FeRu(CO)<inf>6</inf>(R-Pyca) and Fe<inf>2</inf>Ru(CO)<inf>10</inf>(R-Pyca)(R-PycaC<inf>5</inf>H<inf>4</inf>N-2-CHNR); <sup>13</sup>C NMR study of the fluxional behaviour of the carbonyl ligands in Fe<inf>2</inf>Ru(CO)<inf>10</inf>(R-Pyca)
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FeRu(CO)₆(ⁱPr-Pyca) (1a) reacts with hydrogen to give the highly reactive species H₂FeRu(CO)₅(ⁱPr-Pyca) (2), which contains a bridging and a terminal hydride atom. Treatment of 2 with CX₄ affords HFeRu(X)(CO)₅(ⁱPr- Pyca) (XCl (3a); I (3b)) in which the terminal hydride has been substituted. Complex 2 reacts back with carbon monoxide to give FeRu(CO)₆(ⁱPr-Pyca) (1a), whereas treatment of 2 with PMe₂Ph gives FeRu(CO)₅(PMe₂Ph)(ⁱPr-Pyca) (4b). Complexes 4 can easily be prepared from the hexacarbonyl complexes FeRu(CO)₆(α-diimine) (α-diimineⁱPr-Pyca (1a); ⁱPR-DAB (1b)) and the appropriate phosphine, giving FeRu(CO)₅(PR₃)(α-diimine) (α-diimineⁱPr-Pyca, PR₃PPh₃ (4a); α-diimineⁱPr-Pyca, PR₃PMe₂Ph (4b); α- diimineⁱPr-DAB, PR₃PPh₃ (4c); α-diimineⁱPr-DAB, PR₃PMe₂Ph (4d)) in high yields. Reaction of FeRu(CO)₅(PPh₃)(ⁱPr-DAB) (4c) with hydrogen at 90 °C yields FeRu(CO)₅(PPh₃)(ⁱPr-N-CH₂CH₂-N-ⁱPr) (5). The use of deuterium showed that the reduction proceeds stereoselectively, giving solely the trans-addition product FeRu(CO)₅(PPh₃)(ⁱPr-N-C(H)(D)C(H)(D)-N-ⁱPr) (5′). Complex 5 can easily be converted by carbon monoxide to FeRu(CO)₆(ⁱPr-N-CH2CH₂-N-ⁱPr) (8). The conversion of 8 to 5 can be performed also, albeit less facile than the conversion of 5 to 8. The hydrogenation of both 1b and 4c was inhibited by carbon monoxide and free triphenylphosphine. In the latter case the new complexes FeRu(CO)₄(PPh₃)₂(α-diimine) (α-diimineⁱPr-Pyca (6a); ⁱPr-DAB (6b)) were formed. A single crystal X-ray structure determination of 6a was obtained. Red crystals of 6a (C₄₉H₄₂N₂O₄P₂FeRu, M_r=941.8, Z=2) are triclinic, space group P $1$ and have cell constants a=11.625(3), b=14.269(3), c=15.963(2) Å, α=90.95(1), β=100.23(1) and γ=101.95(2)°. A total of 5886 reflections was used in the refinement which converged to a final R value of R=0.064. Reaction of MRu(CO)₆(ⁱPr-DAB)(MFe (1b); Ru (1c)) with 40 bar of carbon monoxide at 90 °C afforded Ru(CO)₃(ⁱPr-DAB) and M(CO)₅ (MFe, Ru). Interestingly it was found that reaction of Ru(CO)₃(DAB) with H₂Fe(CO)₄ also produced FeRu(CO)₆(ⁱPr-N-CH₂CH₂-N-ⁱPr) (8), whereas D₂Fe(CO)₄ afforded only the trans deuterated compound FeRu(CO)₆(ⁱPr-N-C(H)(D)C(H)(D)-N-ⁱPr) (8). Finally attention has been focussed on the elucidation of the mechanism of this trans addition of H₂/D₂ to the central CC bond of the coordinated 1,4-diaza-l,3-butadiene.
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Cluster Chemistry. LIX. Stereochemistry of group 15 ligand-substituted derivatives of M<inf>3</inf>(CO)<inf>12</inf> (M = Ru, Os). D. Synthesis and characterisation of some tetra-substituted ruthenium complexes: X-ray structures of Ru<inf>3</inf>(CO)<inf>8</inf>(L)<inf>4</inf> (L = PMe<inf>2</inf>Ph and P(OR)<inf>3</inf>, R = Me, Et and Ph)
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Several tetra-substituted derivatives of Ru₃(CO)₁₂ have been synthesised, and the molecular structures of Ru₃(CO)₈(L)₄ (L = PMe₂Ph and P(OR)₃, R = Me, Et, Ph) have been determined by single-crystal X-ray diffraction methods. The non-carbonyl ligands occupy equatorial positions in the Ru₃ triangle, one on each of two metal atoms, and two on the third. Twisting of the ML₄ moieties about the RuRu bonds is found, leading to the presence of one μ-CO ligand in the PMe₂Ph and P(OEt)₃ complexes; the latter also has two semi-bridging CO ligands about the other two RuRu bonds. The PMe₂Ph and P(OEt)₃ complexes exhibit $5050$ disorder of the Ru₃ core about a crystallographic inversion centre; the P(OMe)₃ complex has a similar $1585$ disorder in the Ru₃ core, and also in two of the OMe groups on one P(OMe)₃ ligand. A discussion of the major structural features of M₃(CO)_12−n(L)_n (n = 1–4) is given.
Crystal data: Ru₃(CO)₈(PMe₂Ph)₄, triclinic, P $1$ , a 12.040(2), b 10.482(6), c 9.549(4) Å, α 86.26(4), β 69.69(3), γ 78.72(3)°, U 1108.4(6) Å³, Z = 1, N₀ (number of observed data with I > 3σ(I)) = 2056, R = 0.076, R′ = 0.075; Ru₃(CO)₈{P(OMe)₃}₄, monoclinic, P2₁, a 9.821(2), b 17.384(6), c 10.912(3) Å, β 94.88(2)°, U 1856(1) Å³, Z = 2, N_o = 2726, R = 0.041, R′ = 0.046: Ru₃(CO)₈{P(OEt)₂}₄, monoclinic, C2/c, a 18.987(6), b 12.465(4), c 22.244(7) Å, β 102.03(3)°, U 5149(3) Å³, Z = 4, N₀ (I > 2σ(I) = 1729, R = 0.066, R′ = 0.048; Ru₃(CO)₈{P(OPh)₃}₄, monoclinic, P2₁/c, a 21.14(1), b 13.820(9), c 27.24(3) Å, β 106.34(6)°, U 7637(7) Å³, Z = 4, N₀ (I > 2σ(I)) = 6107, R = 0.073, R′ = 0.052.

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Ligand substitution of FeRu2(CO)12 and Fe2Ru(CO)12 with tertiary phosphines and phosphites

Abstract

Adv. Organomet. Chem.

J. Organomet. Chem.

Comp. Organomet. Chem.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Chem. Ind.

Inorg. Chem.

J. Chem. Soc., (A)

Acta Chem. Scan., A

Ligand substitution of FeRu₂(CO)₁₂ and Fe₂Ru(CO)₁₂ with tertiary phosphines and phosphites