Actinide metallocene hydride chemistry: C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η5-C 5Me3H(CH2)-κc ]2- tuck-over ligands in a tetrathorium octahydride complex

Nathan A. Siladke; Christopher L. Webster; Justin R. Walensky; Michael K. Takase; Joseph W. Ziller; Daniel J. Grant; Laura Gagliardi; William J. Evans

doi:10.1021/om4008482

Actinide metallocene hydride chemistry: C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η⁵-C ₅Me₃H(CH₂)-κc ]^2- tuck-over ligands in a tetrathorium octahydride complex

Nathan A. Siladke, Christopher L. Webster, Justin R. Walensky, Michael K. Takase, Joseph W. Ziller, Daniel J. Grant, Laura Gagliardi, William J. Evans

Chemistry (Twin Cities)

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63 Scopus citations

Abstract

Hydrogenolysis of the dimethyl actinide metallocenes (C₅Me ₄SiMe₃)₂UMe₂ and (C ₅Me₄H)₂AnMe₂ (An = Th, U) was examined for comparison with the hydrogenolysis of (C₅Me ₅)₂AnMe₂ that forms the hydrides [(C ₅Me₅)₂ThH₂]₂, [(C ₅Me₅)₂UH₂]₂, and [(C ₅Me₅)₂UH]₂. Parallel reactivity is not found with the (C₅Me₄SiMe₃)^- and (C₅Me₄H)^- complexes. Instead, this study led to the first example of a "tuck-over" [μ-η⁵-C ₅Me₃H(CH₂)-κC]^2- dianion derived from (C₅Me₄H)^- ligands by C-H bond activation and rare examples of a polymetallic thorium polyhydride compound and an organometallic Th³⁺ complex. (C₅Me₄SiMe ₃)₂UMe₂ reacts with H₂ to form the bis(tethered alkyl) complex (η⁵-C₅Me ₄SiMe₂CH₂-κC)₂U, a product of C-H bond activation of the silylmethyl groups. The only identifiable product of hydrogenolysis of (C₅Me₄H)₂UMe₂ is (C₅Me₄H)₃U. The first thorium complex of (C₅Me₄H)^- was synthesized by reaction of 2 equiv of (C₅Me₄H)MgCl(THF) with ThBr₄(THF) ₄ to produce (C₅Me₄H)₂ThBr ₂. This complex reacts with MeLi to make (C₅Me ₄H)₂ThMe₂. The latter complex reacts with H₂ to form the ligand redistribution product (C₅Me ₄H)₃ThMe and the tetrametallic octahydride tuck-over complex (C₅Me₄H)₄[μ-η⁵-C ₅Me₃H(CH₂)-κC]₂Th ₄(μ-H)₄(μ₃-H)₄. For comparison with the (C₅Me₄H)₃U product, the thorium analogue, (C₅Me₄H)₃Th, was synthesized by potassium reduction of a [(C₅Me₄H)₃Th][BPh ₄] intermediate obtained in situ from (C₅Me ₄H)₃ThMe and [HNEt₃][BPh₄]. (C ₅Me₄H)₃Th can also be prepared from KC ₈ and (C₅Me₄H)₃ThBr, obtained from KC₅Me₄H and ThBr₄(THF)₄.

Original language	English (US)
Pages (from-to)	6522-6531
Number of pages	10
Journal	Organometallics
Volume	32
Issue number	21
DOIs	https://doi.org/10.1021/om4008482
State	Published - Nov 11 2013

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10.1021/om4008482

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Siladke, N. A., Webster, C. L., Walensky, J. R., Takase, M. K., Ziller, J. W., Grant, D. J., Gagliardi, L., & Evans, W. J. (2013). Actinide metallocene hydride chemistry: C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η⁵-C ₅Me₃H(CH₂)-κc ]^2- tuck-over ligands in a tetrathorium octahydride complex. Organometallics, 32(21), 6522-6531. https://doi.org/10.1021/om4008482

Actinide metallocene hydride chemistry: C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η⁵-C ₅Me₃H(CH₂)-κc ]^2- tuck-over ligands in a tetrathorium octahydride complex. / Siladke, Nathan A.; Webster, Christopher L.; Walensky, Justin R. et al.
In: Organometallics, Vol. 32, No. 21, 11.11.2013, p. 6522-6531.

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

Siladke, NA, Webster, CL, Walensky, JR, Takase, MK, Ziller, JW, Grant, DJ, Gagliardi, L & Evans, WJ 2013, 'Actinide metallocene hydride chemistry: C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η⁵-C ₅Me₃H(CH₂)-κc ]^2- tuck-over ligands in a tetrathorium octahydride complex', Organometallics, vol. 32, no. 21, pp. 6522-6531. https://doi.org/10.1021/om4008482

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title = "Actinide metallocene hydride chemistry: C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η5-C 5Me3H(CH2)-κc ]2- tuck-over ligands in a tetrathorium octahydride complex",

abstract = "Hydrogenolysis of the dimethyl actinide metallocenes (C5Me 4SiMe3)2UMe2 and (C 5Me4H)2AnMe2 (An = Th, U) was examined for comparison with the hydrogenolysis of (C5Me 5)2AnMe2 that forms the hydrides [(C 5Me5)2ThH2]2, [(C 5Me5)2UH2]2, and [(C 5Me5)2UH]2. Parallel reactivity is not found with the (C5Me4SiMe3)- and (C5Me4H)- complexes. Instead, this study led to the first example of a {"}tuck-over{"} [μ-η5-C 5Me3H(CH2)-κC]2- dianion derived from (C5Me4H)- ligands by C-H bond activation and rare examples of a polymetallic thorium polyhydride compound and an organometallic Th3+ complex. (C5Me4SiMe 3)2UMe2 reacts with H2 to form the bis(tethered alkyl) complex (η5-C5Me 4SiMe2CH2-κC)2U, a product of C-H bond activation of the silylmethyl groups. The only identifiable product of hydrogenolysis of (C5Me4H)2UMe2 is (C5Me4H)3U. The first thorium complex of (C5Me4H)- was synthesized by reaction of 2 equiv of (C5Me4H)MgCl(THF) with ThBr4(THF) 4 to produce (C5Me4H)2ThBr 2. This complex reacts with MeLi to make (C5Me 4H)2ThMe2. The latter complex reacts with H2 to form the ligand redistribution product (C5Me 4H)3ThMe and the tetrametallic octahydride tuck-over complex (C5Me4H)4[μ-η5-C 5Me3H(CH2)-κC]2Th 4(μ-H)4(μ3-H)4. For comparison with the (C5Me4H)3U product, the thorium analogue, (C5Me4H)3Th, was synthesized by potassium reduction of a [(C5Me4H)3Th][BPh 4] intermediate obtained in situ from (C5Me 4H)3ThMe and [HNEt3][BPh4]. (C 5Me4H)3Th can also be prepared from KC 8 and (C5Me4H)3ThBr, obtained from KC5Me4H and ThBr4(THF)4.",

author = "Siladke, {Nathan A.} and Webster, {Christopher L.} and Walensky, {Justin R.} and Takase, {Michael K.} and Ziller, {Joseph W.} and Grant, {Daniel J.} and Laura Gagliardi and Evans, {William J.}",

year = "2013",

month = nov,

day = "11",

doi = "10.1021/om4008482",

language = "English (US)",

volume = "32",

pages = "6522--6531",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "21",

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TY - JOUR

T1 - Actinide metallocene hydride chemistry

T2 - C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η5-C 5Me3H(CH2)-κc ]2- tuck-over ligands in a tetrathorium octahydride complex

AU - Siladke, Nathan A.

AU - Webster, Christopher L.

AU - Walensky, Justin R.

AU - Takase, Michael K.

AU - Ziller, Joseph W.

AU - Grant, Daniel J.

AU - Gagliardi, Laura

AU - Evans, William J.

PY - 2013/11/11

Y1 - 2013/11/11

N2 - Hydrogenolysis of the dimethyl actinide metallocenes (C5Me 4SiMe3)2UMe2 and (C 5Me4H)2AnMe2 (An = Th, U) was examined for comparison with the hydrogenolysis of (C5Me 5)2AnMe2 that forms the hydrides [(C 5Me5)2ThH2]2, [(C 5Me5)2UH2]2, and [(C 5Me5)2UH]2. Parallel reactivity is not found with the (C5Me4SiMe3)- and (C5Me4H)- complexes. Instead, this study led to the first example of a "tuck-over" [μ-η5-C 5Me3H(CH2)-κC]2- dianion derived from (C5Me4H)- ligands by C-H bond activation and rare examples of a polymetallic thorium polyhydride compound and an organometallic Th3+ complex. (C5Me4SiMe 3)2UMe2 reacts with H2 to form the bis(tethered alkyl) complex (η5-C5Me 4SiMe2CH2-κC)2U, a product of C-H bond activation of the silylmethyl groups. The only identifiable product of hydrogenolysis of (C5Me4H)2UMe2 is (C5Me4H)3U. The first thorium complex of (C5Me4H)- was synthesized by reaction of 2 equiv of (C5Me4H)MgCl(THF) with ThBr4(THF) 4 to produce (C5Me4H)2ThBr 2. This complex reacts with MeLi to make (C5Me 4H)2ThMe2. The latter complex reacts with H2 to form the ligand redistribution product (C5Me 4H)3ThMe and the tetrametallic octahydride tuck-over complex (C5Me4H)4[μ-η5-C 5Me3H(CH2)-κC]2Th 4(μ-H)4(μ3-H)4. For comparison with the (C5Me4H)3U product, the thorium analogue, (C5Me4H)3Th, was synthesized by potassium reduction of a [(C5Me4H)3Th][BPh 4] intermediate obtained in situ from (C5Me 4H)3ThMe and [HNEt3][BPh4]. (C 5Me4H)3Th can also be prepared from KC 8 and (C5Me4H)3ThBr, obtained from KC5Me4H and ThBr4(THF)4.

AB - Hydrogenolysis of the dimethyl actinide metallocenes (C5Me 4SiMe3)2UMe2 and (C 5Me4H)2AnMe2 (An = Th, U) was examined for comparison with the hydrogenolysis of (C5Me 5)2AnMe2 that forms the hydrides [(C 5Me5)2ThH2]2, [(C 5Me5)2UH2]2, and [(C 5Me5)2UH]2. Parallel reactivity is not found with the (C5Me4SiMe3)- and (C5Me4H)- complexes. Instead, this study led to the first example of a "tuck-over" [μ-η5-C 5Me3H(CH2)-κC]2- dianion derived from (C5Me4H)- ligands by C-H bond activation and rare examples of a polymetallic thorium polyhydride compound and an organometallic Th3+ complex. (C5Me4SiMe 3)2UMe2 reacts with H2 to form the bis(tethered alkyl) complex (η5-C5Me 4SiMe2CH2-κC)2U, a product of C-H bond activation of the silylmethyl groups. The only identifiable product of hydrogenolysis of (C5Me4H)2UMe2 is (C5Me4H)3U. The first thorium complex of (C5Me4H)- was synthesized by reaction of 2 equiv of (C5Me4H)MgCl(THF) with ThBr4(THF) 4 to produce (C5Me4H)2ThBr 2. This complex reacts with MeLi to make (C5Me 4H)2ThMe2. The latter complex reacts with H2 to form the ligand redistribution product (C5Me 4H)3ThMe and the tetrametallic octahydride tuck-over complex (C5Me4H)4[μ-η5-C 5Me3H(CH2)-κC]2Th 4(μ-H)4(μ3-H)4. For comparison with the (C5Me4H)3U product, the thorium analogue, (C5Me4H)3Th, was synthesized by potassium reduction of a [(C5Me4H)3Th][BPh 4] intermediate obtained in situ from (C5Me 4H)3ThMe and [HNEt3][BPh4]. (C 5Me4H)3Th can also be prepared from KC 8 and (C5Me4H)3ThBr, obtained from KC5Me4H and ThBr4(THF)4.

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Actinide metallocene hydride chemistry: C-H activation in tetramethylcyclopentadienyl ligands to form [μ-η⁵-C ₅Me₃H(CH₂)-κc ]^2- tuck-over ligands in a tetrathorium octahydride complex

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