Tethered indenyl-phosphine complexes of ruthenium(II) via reductive elimination of a ruthenium(IV) complex

Sin Yee Ng; Geok Kheng Tan; Lip Lin Koh; Weng Kee Leong; Lai Yoong Goh

doi:10.1021/om070225j

Tethered indenyl-phosphine complexes of ruthenium(II) via reductive elimination of a ruthenium(IV) complex

Sin Yee Ng, Geok Kheng Tan, Lip Lin Koh, Weng Kee Leong^*, Lai Yoong Goh

^*Corresponding author for this work

National University of Singapore

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

16 Citations (Scopus)

Abstract

The Ru(IV) phosphine complex [(η³,η³-C ₁₀H₁₆)RuCl₂(κ¹P-LH)] (2) was synthesized from the reaction of [(η³,η³-C ₁₀H₁₆)RuCl₂]₂ with [(C ₉H₇)(CH₂)₂PPh₂] (LH). Treatment of 2 with acid led to halide labilization to give [(η ³η³-C₁₀H₁₆)RuCl(CH ₃CN)(κ¹-LH)]⁺ [2a]⁺. Reductive elimination of the bis(allyl) ligand in 2 was effected in the reaction of 2, a two- or four-electron ligand (DD), Na₂CO₃, and KPF ₆ in EtOH, resulting in the isolation of PF₆ salts of monocationic tethered indenyl Ru species, [(η,κ¹P-L)Ru(DD)] (3, DD = 1,5-cyclooctadiene (COD); 6, DD = 2,2′-bipyridyl (bpy)), and neutral tethered indenyl Ru complexes (4, DD = (PPh₃)Cl; 5, DD = (PPh₃)H). In addition to [6]PF₆, [(κ¹P- LH)Ru(bpy)₂Cl]PF₆, [7]PF₆, was an additional product in the bpy reaction, as was {[(κ¹P-LH)Ru(bpy)Cl] ₂(μ-Cl)₃}PF₆, [8]-PF₆, when Na₂CO₃ was replaced by Li₂CO₃. In the presence of HC1, [6]⁺ was found to convert to [8]⁺, while [8]⁺ was converted to [7]⁺ with bpy and KPF ₆. The reaction of 2 with acetylacetone (acacH) gave a high yield of an unusual complex, [(η²,κ¹P-LH)Ru(acac) ₂] (9), in which LH adopts a rare η², κ¹P-coordination mode. The new compounds were all spectroscopically characterized, with 2, 2a, 3, 4, and 9 also determined by single-crystal X-ray diffraction analyses.

Original language	English
Pages (from-to)	3352-3361
Number of pages	10
Journal	Organometallics
Volume	26
Issue number	14
DOIs	https://doi.org/10.1021/om070225j
Publication status	Published - Jul 2 2007
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{85c05e21329b498f9dd1b13f517497dc,

title = "Tethered indenyl-phosphine complexes of ruthenium(II) via reductive elimination of a ruthenium(IV) complex",

abstract = "The Ru(IV) phosphine complex [(η3,η3-C 10H16)RuCl2(κ1P-LH)] (2) was synthesized from the reaction of [(η3,η3-C 10H16)RuCl2]2 with [(C 9H7)(CH2)2PPh2] (LH). Treatment of 2 with acid led to halide labilization to give [(η 3η3-C10H16)RuCl(CH 3CN)(κ1-LH)]+ [2a]+. Reductive elimination of the bis(allyl) ligand in 2 was effected in the reaction of 2, a two- or four-electron ligand (DD), Na2CO3, and KPF 6 in EtOH, resulting in the isolation of PF6 salts of monocationic tethered indenyl Ru species, [(η,κ1P-L)Ru(DD)] (3, DD = 1,5-cyclooctadiene (COD); 6, DD = 2,2′-bipyridyl (bpy)), and neutral tethered indenyl Ru complexes (4, DD = (PPh3)Cl; 5, DD = (PPh3)H). In addition to [6]PF6, [(κ1P- LH)Ru(bpy)2Cl]PF6, [7]PF6, was an additional product in the bpy reaction, as was {[(κ1P-LH)Ru(bpy)Cl] 2(μ-Cl)3}PF6, [8]-PF6, when Na2CO3 was replaced by Li2CO3. In the presence of HC1, [6]+ was found to convert to [8]+, while [8]+ was converted to [7]+ with bpy and KPF 6. The reaction of 2 with acetylacetone (acacH) gave a high yield of an unusual complex, [(η2,κ1P-LH)Ru(acac) 2] (9), in which LH adopts a rare η2, κ1P-coordination mode. The new compounds were all spectroscopically characterized, with 2, 2a, 3, 4, and 9 also determined by single-crystal X-ray diffraction analyses.",

author = "Ng, {Sin Yee} and Tan, {Geok Kheng} and Koh, {Lip Lin} and Leong, {Weng Kee} and Goh, {Lai Yoong}",

year = "2007",

month = jul,

day = "2",

doi = "10.1021/om070225j",

language = "English",

volume = "26",

pages = "3352--3361",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "14",

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TY - JOUR

T1 - Tethered indenyl-phosphine complexes of ruthenium(II) via reductive elimination of a ruthenium(IV) complex

AU - Ng, Sin Yee

AU - Tan, Geok Kheng

AU - Koh, Lip Lin

AU - Leong, Weng Kee

AU - Goh, Lai Yoong

PY - 2007/7/2

Y1 - 2007/7/2

N2 - The Ru(IV) phosphine complex [(η3,η3-C 10H16)RuCl2(κ1P-LH)] (2) was synthesized from the reaction of [(η3,η3-C 10H16)RuCl2]2 with [(C 9H7)(CH2)2PPh2] (LH). Treatment of 2 with acid led to halide labilization to give [(η 3η3-C10H16)RuCl(CH 3CN)(κ1-LH)]+ [2a]+. Reductive elimination of the bis(allyl) ligand in 2 was effected in the reaction of 2, a two- or four-electron ligand (DD), Na2CO3, and KPF 6 in EtOH, resulting in the isolation of PF6 salts of monocationic tethered indenyl Ru species, [(η,κ1P-L)Ru(DD)] (3, DD = 1,5-cyclooctadiene (COD); 6, DD = 2,2′-bipyridyl (bpy)), and neutral tethered indenyl Ru complexes (4, DD = (PPh3)Cl; 5, DD = (PPh3)H). In addition to [6]PF6, [(κ1P- LH)Ru(bpy)2Cl]PF6, [7]PF6, was an additional product in the bpy reaction, as was {[(κ1P-LH)Ru(bpy)Cl] 2(μ-Cl)3}PF6, [8]-PF6, when Na2CO3 was replaced by Li2CO3. In the presence of HC1, [6]+ was found to convert to [8]+, while [8]+ was converted to [7]+ with bpy and KPF 6. The reaction of 2 with acetylacetone (acacH) gave a high yield of an unusual complex, [(η2,κ1P-LH)Ru(acac) 2] (9), in which LH adopts a rare η2, κ1P-coordination mode. The new compounds were all spectroscopically characterized, with 2, 2a, 3, 4, and 9 also determined by single-crystal X-ray diffraction analyses.

AB - The Ru(IV) phosphine complex [(η3,η3-C 10H16)RuCl2(κ1P-LH)] (2) was synthesized from the reaction of [(η3,η3-C 10H16)RuCl2]2 with [(C 9H7)(CH2)2PPh2] (LH). Treatment of 2 with acid led to halide labilization to give [(η 3η3-C10H16)RuCl(CH 3CN)(κ1-LH)]+ [2a]+. Reductive elimination of the bis(allyl) ligand in 2 was effected in the reaction of 2, a two- or four-electron ligand (DD), Na2CO3, and KPF 6 in EtOH, resulting in the isolation of PF6 salts of monocationic tethered indenyl Ru species, [(η,κ1P-L)Ru(DD)] (3, DD = 1,5-cyclooctadiene (COD); 6, DD = 2,2′-bipyridyl (bpy)), and neutral tethered indenyl Ru complexes (4, DD = (PPh3)Cl; 5, DD = (PPh3)H). In addition to [6]PF6, [(κ1P- LH)Ru(bpy)2Cl]PF6, [7]PF6, was an additional product in the bpy reaction, as was {[(κ1P-LH)Ru(bpy)Cl] 2(μ-Cl)3}PF6, [8]-PF6, when Na2CO3 was replaced by Li2CO3. In the presence of HC1, [6]+ was found to convert to [8]+, while [8]+ was converted to [7]+ with bpy and KPF 6. The reaction of 2 with acetylacetone (acacH) gave a high yield of an unusual complex, [(η2,κ1P-LH)Ru(acac) 2] (9), in which LH adopts a rare η2, κ1P-coordination mode. The new compounds were all spectroscopically characterized, with 2, 2a, 3, 4, and 9 also determined by single-crystal X-ray diffraction analyses.

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ER -

Tethered indenyl-phosphine complexes of ruthenium(II) via reductive elimination of a ruthenium(IV) complex

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