Synthetic and structural study of cyclopentadienylchromium dithiocarbamate complexes and their thermolytic derivatives

Lai Yoong Goh; Zhiqiang Weng; Weng Kee Leong; Pak Hing Leung

doi:10.1021/om0202930

Synthetic and structural study of cyclopentadienylchromium dithiocarbamate complexes and their thermolytic derivatives

Lai Yoong Goh^*, Zhiqiang Weng, Weng Kee Leong, Pak Hing Leung

^*Corresponding author for this work

National University of Singapore

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

33 Citations (Scopus)

Abstract

The reaction of [CpCr(CO)₃]₂ (1) with the tetraalkylthiuram disulfides [R₂NC(S)S]₂ (R = Me, Et, i-Pr) has been investigated. At ambient temperature, CpCr(CO)₂(η²-S₂CNR₂) (3) was obtained as air-stable dark red crystals in 81-87% yields from reactions in solution and in quantitative yield from a reaction in the solid state (3a, R = Me); the precursor complex CpCr(CO)₃(η¹-S₂CNMe₂) (2a) crystallized out in a 1:1 admixture with 3a from a product solution after 3 days at -29 °C. At 90 °C for 2 h, the same reaction or the thermal degradation of 3 led to the isolation of the thiocarbenoid complex CpCr(CO)₂(η²-SCNR₂) (4) as dark red crystals (ca. 10%), double cubanes Cp₆Cr₈S₈(η²:⁴-SCNR ₂)₂ (5a, R = Me; 5b, R = Et) as dark brown crystals (3-7%), Cp₆Cr₆S₈(η¹:η?²-S ₂CNR) (6) as dark crystals (7-14%), Cr(η²-S₂CNR₂)₃ (7) as dark blue crystals (16-21%), Cp₂Cr₂(CO)₄S as dark green crystals (1-3%), and Cp₄Cr₄S₄ (12-22%) as dark green solids. The crystal structures of 2-6 were reported. Unprecedented bridging modes were found in the double cubanes: in 5, two Cr₄S₄ cubane clusters were linked by a μ-η²:η⁴-dithiooxamide ligand as well as a Cr - Cr bridge with bond distances of 3.101 and 3.118 Å in the two independent molecules of the compound, and in 6, the cubanes were linked by two μ-η¹:η²-dithiocarbamate ligands.

Original language	English
Pages (from-to)	4398-4407
Number of pages	10
Journal	Organometallics
Volume	21
Issue number	21
DOIs	https://doi.org/10.1021/om0202930
Publication status	Published - Oct 14 2002
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{16a45df2ab774c4eb260e136da2a376f,

title = "Synthetic and structural study of cyclopentadienylchromium dithiocarbamate complexes and their thermolytic derivatives",

abstract = "The reaction of [CpCr(CO)3]2 (1) with the tetraalkylthiuram disulfides [R2NC(S)S]2 (R = Me, Et, i-Pr) has been investigated. At ambient temperature, CpCr(CO)2(η2-S2CNR2) (3) was obtained as air-stable dark red crystals in 81-87% yields from reactions in solution and in quantitative yield from a reaction in the solid state (3a, R = Me); the precursor complex CpCr(CO)3(η1-S2CNMe2) (2a) crystallized out in a 1:1 admixture with 3a from a product solution after 3 days at -29 °C. At 90 °C for 2 h, the same reaction or the thermal degradation of 3 led to the isolation of the thiocarbenoid complex CpCr(CO)2(η2-SCNR2) (4) as dark red crystals (ca. 10%), double cubanes Cp6Cr8S8(η2:4-SCNR 2)2 (5a, R = Me; 5b, R = Et) as dark brown crystals (3-7%), Cp6Cr6S8(η1:η?2-S 2CNR) (6) as dark crystals (7-14%), Cr(η2-S2CNR2)3 (7) as dark blue crystals (16-21%), Cp2Cr2(CO)4S as dark green crystals (1-3%), and Cp4Cr4S4 (12-22%) as dark green solids. The crystal structures of 2-6 were reported. Unprecedented bridging modes were found in the double cubanes: in 5, two Cr4S4 cubane clusters were linked by a μ-η2:η4-dithiooxamide ligand as well as a Cr - Cr bridge with bond distances of 3.101 and 3.118 {\AA} in the two independent molecules of the compound, and in 6, the cubanes were linked by two μ-η1:η2-dithiocarbamate ligands.",

author = "Goh, {Lai Yoong} and Zhiqiang Weng and Leong, {Weng Kee} and Leung, {Pak Hing}",

year = "2002",

month = oct,

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doi = "10.1021/om0202930",

language = "English",

volume = "21",

pages = "4398--4407",

journal = "Organometallics",

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T1 - Synthetic and structural study of cyclopentadienylchromium dithiocarbamate complexes and their thermolytic derivatives

AU - Goh, Lai Yoong

AU - Weng, Zhiqiang

AU - Leong, Weng Kee

AU - Leung, Pak Hing

PY - 2002/10/14

Y1 - 2002/10/14

N2 - The reaction of [CpCr(CO)3]2 (1) with the tetraalkylthiuram disulfides [R2NC(S)S]2 (R = Me, Et, i-Pr) has been investigated. At ambient temperature, CpCr(CO)2(η2-S2CNR2) (3) was obtained as air-stable dark red crystals in 81-87% yields from reactions in solution and in quantitative yield from a reaction in the solid state (3a, R = Me); the precursor complex CpCr(CO)3(η1-S2CNMe2) (2a) crystallized out in a 1:1 admixture with 3a from a product solution after 3 days at -29 °C. At 90 °C for 2 h, the same reaction or the thermal degradation of 3 led to the isolation of the thiocarbenoid complex CpCr(CO)2(η2-SCNR2) (4) as dark red crystals (ca. 10%), double cubanes Cp6Cr8S8(η2:4-SCNR 2)2 (5a, R = Me; 5b, R = Et) as dark brown crystals (3-7%), Cp6Cr6S8(η1:η?2-S 2CNR) (6) as dark crystals (7-14%), Cr(η2-S2CNR2)3 (7) as dark blue crystals (16-21%), Cp2Cr2(CO)4S as dark green crystals (1-3%), and Cp4Cr4S4 (12-22%) as dark green solids. The crystal structures of 2-6 were reported. Unprecedented bridging modes were found in the double cubanes: in 5, two Cr4S4 cubane clusters were linked by a μ-η2:η4-dithiooxamide ligand as well as a Cr - Cr bridge with bond distances of 3.101 and 3.118 Å in the two independent molecules of the compound, and in 6, the cubanes were linked by two μ-η1:η2-dithiocarbamate ligands.

AB - The reaction of [CpCr(CO)3]2 (1) with the tetraalkylthiuram disulfides [R2NC(S)S]2 (R = Me, Et, i-Pr) has been investigated. At ambient temperature, CpCr(CO)2(η2-S2CNR2) (3) was obtained as air-stable dark red crystals in 81-87% yields from reactions in solution and in quantitative yield from a reaction in the solid state (3a, R = Me); the precursor complex CpCr(CO)3(η1-S2CNMe2) (2a) crystallized out in a 1:1 admixture with 3a from a product solution after 3 days at -29 °C. At 90 °C for 2 h, the same reaction or the thermal degradation of 3 led to the isolation of the thiocarbenoid complex CpCr(CO)2(η2-SCNR2) (4) as dark red crystals (ca. 10%), double cubanes Cp6Cr8S8(η2:4-SCNR 2)2 (5a, R = Me; 5b, R = Et) as dark brown crystals (3-7%), Cp6Cr6S8(η1:η?2-S 2CNR) (6) as dark crystals (7-14%), Cr(η2-S2CNR2)3 (7) as dark blue crystals (16-21%), Cp2Cr2(CO)4S as dark green crystals (1-3%), and Cp4Cr4S4 (12-22%) as dark green solids. The crystal structures of 2-6 were reported. Unprecedented bridging modes were found in the double cubanes: in 5, two Cr4S4 cubane clusters were linked by a μ-η2:η4-dithiooxamide ligand as well as a Cr - Cr bridge with bond distances of 3.101 and 3.118 Å in the two independent molecules of the compound, and in 6, the cubanes were linked by two μ-η1:η2-dithiocarbamate ligands.

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Synthetic and structural study of cyclopentadienylchromium dithiocarbamate complexes and their thermolytic derivatives

Abstract

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