### Abstract

This contribution describes thorium hydrocarbyl and hydride chemistry based upon the chelating (CH_{3})_{2}Si[(CH_{3})_{4}C_{5}] _{2}^{2-} ligand (Me_{2}SiCp″_{2}^{2-}). Precursor Me_{2}Si(Cp″H)_{2} can be prepared by reaction of SiCl_{4} with 2 equiv of Li(CH_{3})_{4}C_{5}, followed by methylation (CH_{3}Li) and methanolic workup. Subsequent reaction with n-C_{4}H_{9}Li in 1,2-dimethoxyethane yields Me_{2}Si(Cp″Li)_{2}·2DME. The dilithium salt undergoes reaction with ThCl_{4} to yield Me_{2}SiCp″_{2}ThCl_{2}·2LiCl·2pME, which, in turn, can be alkylated with lithium reagents to produce crystalline, thermally stable Me_{2}SiCp″_{2}ThR_{2} complexes where R = CH_{2}Si(CH_{3})_{3}, CH_{2}C(CH_{3})_{3}, C_{6}H_{5}, n-C_{4}H_{9}, and CH_{2}C_{6}H_{5}. The Me_{2}SiCp″_{2}Th[CH_{2}Si(CH_{3}) _{3}]_{2} complex crystallizes in the monoclinic space group P2_{1}/m - C_{2h}^{2} with two molecules in a unit cell of dimensions (20 ± 1°C) a = 11.960 (5) Å, b = 11.270 (5) Å, c = 12.395 (6) Å, and β = 99.32 (4)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.076 for 2586 independent reflections having I > 3σ(I). The molecular structure consists of monomeric Me_{2}SiCp′_{2}Th[CH_{2}Si(CH_{3}) _{3}]_{2} units with η^{5}-Cp″ coordination and ∠ (ring centroid)-Th-(ring centroid) = 118.4°. There is considerable dispersion in the Th-C(ring) distances. The Th[CH_{2}Si(CH_{3})_{3}]_{2} ligation is highly distorted, with Th-C-Si angles of 123.7 (14)° and 149.5 (12)°, accompanied by corresponding Th-C distances of 2.54 (2) and 2.48 (2) Å, respectively. The thorium coordination sphere is more "open" than that in Cp′_{2}Th[CH_{2}Si(CH_{3})_{3}] _{2}. Hydrogenolysis of the dialkyl yields the dimeric hydride Me_{2}SiCp″Th(μ-H)_{4}ThCp″_{2}SiMe _{2}, which crystallizes in the monoclinic space group P2_{1}/n with four molecules in a unit cell of dimensions (20 ± 1°C) a = 10.965 (2) Å, b = 19.843 (5) Å, c = 18.759 (3) Å, and β = 90.39 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.075 for 3298 independent reflections having I > 3σ(I). The dimer exhibits approximate C_{2} symmetry with (ring centroid)-Th-(ring centroid) angles of 118.1° and 117.7°. The Th-Th distance is 3.632 (2) Å which suggests, in combination with infrared spectral data, a Th(μ-H)_{4}Th structure. The above hydride catalyzes the hydrogenation of 1-hexene at a rate ca. 10^{3} faster than (Cp′_{2}ThH_{2})_{2}. For trans-2-hexene, hydrogenation catalyzed by the ring-bridged hydride is ca. 30 times more rapid than by (Cp_{2}′ThH_{2})_{2}.

Original language | English |
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Pages (from-to) | 1828-1838 |

Number of pages | 11 |

Journal | Organometallics |

Volume | 7 |

Issue number | 8 |

Publication status | Published - 1988 |

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### ASJC Scopus subject areas

- Inorganic Chemistry
- Organic Chemistry

### Cite this

*Organometallics*,

*7*(8), 1828-1838.

**Manipulation of organoactinide coordinative unsaturation. Synthesis, structures, and reactivity of thorium hydrocarbyls and hydrides with chelating bis(tetramethylcyclopentadienyl) ancillary ligands.** / Fendrick, Carol M.; Schertz, Larry D.; Marks, Tobin J; Marks, Tobin J.

Research output: Contribution to journal › Article

*Organometallics*, vol. 7, no. 8, pp. 1828-1838.

}

TY - JOUR

T1 - Manipulation of organoactinide coordinative unsaturation. Synthesis, structures, and reactivity of thorium hydrocarbyls and hydrides with chelating bis(tetramethylcyclopentadienyl) ancillary ligands

AU - Fendrick, Carol M.

AU - Schertz, Larry D.

AU - Marks, Tobin J

AU - Marks, Tobin J.

PY - 1988

Y1 - 1988

N2 - This contribution describes thorium hydrocarbyl and hydride chemistry based upon the chelating (CH3)2Si[(CH3)4C5] 22- ligand (Me2SiCp″22-). Precursor Me2Si(Cp″H)2 can be prepared by reaction of SiCl4 with 2 equiv of Li(CH3)4C5, followed by methylation (CH3Li) and methanolic workup. Subsequent reaction with n-C4H9Li in 1,2-dimethoxyethane yields Me2Si(Cp″Li)2·2DME. The dilithium salt undergoes reaction with ThCl4 to yield Me2SiCp″2ThCl2·2LiCl·2pME, which, in turn, can be alkylated with lithium reagents to produce crystalline, thermally stable Me2SiCp″2ThR2 complexes where R = CH2Si(CH3)3, CH2C(CH3)3, C6H5, n-C4H9, and CH2C6H5. The Me2SiCp″2Th[CH2Si(CH3) 3]2 complex crystallizes in the monoclinic space group P21/m - C2h2 with two molecules in a unit cell of dimensions (20 ± 1°C) a = 11.960 (5) Å, b = 11.270 (5) Å, c = 12.395 (6) Å, and β = 99.32 (4)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.076 for 2586 independent reflections having I > 3σ(I). The molecular structure consists of monomeric Me2SiCp′2Th[CH2Si(CH3) 3]2 units with η5-Cp″ coordination and ∠ (ring centroid)-Th-(ring centroid) = 118.4°. There is considerable dispersion in the Th-C(ring) distances. The Th[CH2Si(CH3)3]2 ligation is highly distorted, with Th-C-Si angles of 123.7 (14)° and 149.5 (12)°, accompanied by corresponding Th-C distances of 2.54 (2) and 2.48 (2) Å, respectively. The thorium coordination sphere is more "open" than that in Cp′2Th[CH2Si(CH3)3] 2. Hydrogenolysis of the dialkyl yields the dimeric hydride Me2SiCp″Th(μ-H)4ThCp″2SiMe 2, which crystallizes in the monoclinic space group P21/n with four molecules in a unit cell of dimensions (20 ± 1°C) a = 10.965 (2) Å, b = 19.843 (5) Å, c = 18.759 (3) Å, and β = 90.39 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.075 for 3298 independent reflections having I > 3σ(I). The dimer exhibits approximate C2 symmetry with (ring centroid)-Th-(ring centroid) angles of 118.1° and 117.7°. The Th-Th distance is 3.632 (2) Å which suggests, in combination with infrared spectral data, a Th(μ-H)4Th structure. The above hydride catalyzes the hydrogenation of 1-hexene at a rate ca. 103 faster than (Cp′2ThH2)2. For trans-2-hexene, hydrogenation catalyzed by the ring-bridged hydride is ca. 30 times more rapid than by (Cp2′ThH2)2.

AB - This contribution describes thorium hydrocarbyl and hydride chemistry based upon the chelating (CH3)2Si[(CH3)4C5] 22- ligand (Me2SiCp″22-). Precursor Me2Si(Cp″H)2 can be prepared by reaction of SiCl4 with 2 equiv of Li(CH3)4C5, followed by methylation (CH3Li) and methanolic workup. Subsequent reaction with n-C4H9Li in 1,2-dimethoxyethane yields Me2Si(Cp″Li)2·2DME. The dilithium salt undergoes reaction with ThCl4 to yield Me2SiCp″2ThCl2·2LiCl·2pME, which, in turn, can be alkylated with lithium reagents to produce crystalline, thermally stable Me2SiCp″2ThR2 complexes where R = CH2Si(CH3)3, CH2C(CH3)3, C6H5, n-C4H9, and CH2C6H5. The Me2SiCp″2Th[CH2Si(CH3) 3]2 complex crystallizes in the monoclinic space group P21/m - C2h2 with two molecules in a unit cell of dimensions (20 ± 1°C) a = 11.960 (5) Å, b = 11.270 (5) Å, c = 12.395 (6) Å, and β = 99.32 (4)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.076 for 2586 independent reflections having I > 3σ(I). The molecular structure consists of monomeric Me2SiCp′2Th[CH2Si(CH3) 3]2 units with η5-Cp″ coordination and ∠ (ring centroid)-Th-(ring centroid) = 118.4°. There is considerable dispersion in the Th-C(ring) distances. The Th[CH2Si(CH3)3]2 ligation is highly distorted, with Th-C-Si angles of 123.7 (14)° and 149.5 (12)°, accompanied by corresponding Th-C distances of 2.54 (2) and 2.48 (2) Å, respectively. The thorium coordination sphere is more "open" than that in Cp′2Th[CH2Si(CH3)3] 2. Hydrogenolysis of the dialkyl yields the dimeric hydride Me2SiCp″Th(μ-H)4ThCp″2SiMe 2, which crystallizes in the monoclinic space group P21/n with four molecules in a unit cell of dimensions (20 ± 1°C) a = 10.965 (2) Å, b = 19.843 (5) Å, c = 18.759 (3) Å, and β = 90.39 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.075 for 3298 independent reflections having I > 3σ(I). The dimer exhibits approximate C2 symmetry with (ring centroid)-Th-(ring centroid) angles of 118.1° and 117.7°. The Th-Th distance is 3.632 (2) Å which suggests, in combination with infrared spectral data, a Th(μ-H)4Th structure. The above hydride catalyzes the hydrogenation of 1-hexene at a rate ca. 103 faster than (Cp′2ThH2)2. For trans-2-hexene, hydrogenation catalyzed by the ring-bridged hydride is ca. 30 times more rapid than by (Cp2′ThH2)2.

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M3 - Article

AN - SCOPUS:33845280501

VL - 7

SP - 1828

EP - 1838

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 8

ER -