Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)2(S2P(OR)2), CpCr(S2P(OR)2)2 and Cr(S2P(OR)2)3 (R=iPr)

Lai Yoong Goh; Zhiqiang Weng; Weng Kee Leong; Ionel Haiduc; Kong Mun Lo; Richard C.S. Wong

doi:10.1016/S0022-328X(01)01031-2

Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)₂(S₂P(OR)₂), CpCr(S₂P(OR)₂)₂ and Cr(S₂P(OR)₂)₃ (R=ⁱPr)

Lai Yoong Goh^*, Zhiqiang Weng, Weng Kee Leong, Ionel Haiduc, Kong Mun Lo, Richard C.S. Wong

^*Corresponding author for this work

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

15 Citations (Scopus)

Abstract

The facile reaction of [CpCr(CO)₃]₂ (Cp=η⁵-C₅H₅) with one mole equivalent of bis(thiophosphoryl)disulfanes, (RO)₂P(S)SSP(S)(OR)₂ (R=ⁱPr), at ambient temperature, led to the isolation of dark-purple solids of CpCr(CO)₂(S₂P(OR)₂) (2, yield: 32%) and blue solids of CpCr(S₂P(OR)₂)₂ (3, yield: 30%). At 70-80°C, the reaction gave 3 (yield: 35%) and Cr(S₂P(OR)₂)₃ (4, yield: 11%). ¹H-NMR spectral studies demonstrated that 3 and 4 were derived from 2, the primary product. X-ray diffraction analyses showed that 2 possesses cis CO ligands and a bidentate SP(S)(OR)₂ ligand, while 3 contains both an unidentate and a bidentate ligand, and in 4 the Cr atom is octahedrally symmetrically coordinated to the three bidentate phosphorylthioato ligand. Variable temperature ¹H and ³¹P spectral studies showed the occurrence of very rapid unidentate-bidentate exchange between the ligands in 3 in the temperature range -65 to 80°C. It is also shown that the CrCr complex [CpCr(CO)₂]₂ reacted with [(ⁱPrO)₂P(S)S]₂, albeit much less readily, generating 3 as the eventual product.

Original language	English
Pages (from-to)	67-75
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	631
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(01)01031-2
Publication status	Published - Aug 10 2001
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

15-Electron chromium(III)
Crystal structures
Cyclopentadienylchromium
Di-isopropyldithiophosphate
Phosphorodithioato

Access to Document

10.1016/S0022-328X(01)01031-2

Fingerprint

Dive into the research topics of 'Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)₂(S₂P(OR)₂), CpCr(S₂P(OR)₂)₂ and Cr(S₂P(OR)₂)₃ (R=ⁱPr)'. Together they form a unique fingerprint.

Cite this

Goh, L. Y., Weng, Z., Leong, W. K., Haiduc, I., Lo, K. M., & Wong, R. C. S. (2001). Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)₂(S₂P(OR)₂), CpCr(S₂P(OR)₂)₂ and Cr(S₂P(OR)₂)₃ (R=ⁱPr). Journal of Organometallic Chemistry, 631(1-2), 67-75. https://doi.org/10.1016/S0022-328X(01)01031-2

@article{7d6db21c08dd4dafb25d3ca1aad8e789,

title = "Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)2(S2P(OR)2), CpCr(S2P(OR)2)2 and Cr(S2P(OR)2)3 (R=iPr)",

abstract = "The facile reaction of [CpCr(CO)3]2 (Cp=η5-C5H5) with one mole equivalent of bis(thiophosphoryl)disulfanes, (RO)2P(S)SSP(S)(OR)2 (R=iPr), at ambient temperature, led to the isolation of dark-purple solids of CpCr(CO)2(S2P(OR)2) (2, yield: 32%) and blue solids of CpCr(S2P(OR)2)2 (3, yield: 30%). At 70-80°C, the reaction gave 3 (yield: 35%) and Cr(S2P(OR)2)3 (4, yield: 11%). 1H-NMR spectral studies demonstrated that 3 and 4 were derived from 2, the primary product. X-ray diffraction analyses showed that 2 possesses cis CO ligands and a bidentate SP(S)(OR)2 ligand, while 3 contains both an unidentate and a bidentate ligand, and in 4 the Cr atom is octahedrally symmetrically coordinated to the three bidentate phosphorylthioato ligand. Variable temperature 1H and 31P spectral studies showed the occurrence of very rapid unidentate-bidentate exchange between the ligands in 3 in the temperature range -65 to 80°C. It is also shown that the CrCr complex [CpCr(CO)2]2 reacted with [(iPrO)2P(S)S]2, albeit much less readily, generating 3 as the eventual product.",

keywords = "15-Electron chromium(III), Crystal structures, Cyclopentadienylchromium, Di-isopropyldithiophosphate, Phosphorodithioato",

author = "Goh, {Lai Yoong} and Zhiqiang Weng and Leong, {Weng Kee} and Ionel Haiduc and Lo, {Kong Mun} and Wong, {Richard C.S.}",

year = "2001",

month = aug,

day = "10",

doi = "10.1016/S0022-328X(01)01031-2",

language = "English",

volume = "631",

pages = "67--75",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

}

Goh, LY, Weng, Z, Leong, WK, Haiduc, I, Lo, KM & Wong, RCS 2001, 'Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)₂(S₂P(OR)₂), CpCr(S₂P(OR)₂)₂ and Cr(S₂P(OR)₂)₃ (R=ⁱPr)', Journal of Organometallic Chemistry, vol. 631, no. 1-2, pp. 67-75. https://doi.org/10.1016/S0022-328X(01)01031-2

Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)₂(S₂P(OR)₂), CpCr(S₂P(OR)₂)₂ and Cr(S₂P(OR)₂)₃ (R=ⁱPr). / Goh, Lai Yoong; Weng, Zhiqiang; Leong, Weng Kee et al.
In: Journal of Organometallic Chemistry, Vol. 631, No. 1-2, 10.08.2001, p. 67-75.

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

TY - JOUR

T1 - Chemistry of cyclopentadienyl tricarbonylchromium dimer. Cleavage of bis(thiophosphoryl)disulfanes. Syntheses and X-ray crystal structures of CpCr(CO)2(S2P(OR)2), CpCr(S2P(OR)2)2 and Cr(S2P(OR)2)3 (R=iPr)

AU - Goh, Lai Yoong

AU - Weng, Zhiqiang

AU - Leong, Weng Kee

AU - Haiduc, Ionel

AU - Lo, Kong Mun

AU - Wong, Richard C.S.

PY - 2001/8/10

Y1 - 2001/8/10

N2 - The facile reaction of [CpCr(CO)3]2 (Cp=η5-C5H5) with one mole equivalent of bis(thiophosphoryl)disulfanes, (RO)2P(S)SSP(S)(OR)2 (R=iPr), at ambient temperature, led to the isolation of dark-purple solids of CpCr(CO)2(S2P(OR)2) (2, yield: 32%) and blue solids of CpCr(S2P(OR)2)2 (3, yield: 30%). At 70-80°C, the reaction gave 3 (yield: 35%) and Cr(S2P(OR)2)3 (4, yield: 11%). 1H-NMR spectral studies demonstrated that 3 and 4 were derived from 2, the primary product. X-ray diffraction analyses showed that 2 possesses cis CO ligands and a bidentate SP(S)(OR)2 ligand, while 3 contains both an unidentate and a bidentate ligand, and in 4 the Cr atom is octahedrally symmetrically coordinated to the three bidentate phosphorylthioato ligand. Variable temperature 1H and 31P spectral studies showed the occurrence of very rapid unidentate-bidentate exchange between the ligands in 3 in the temperature range -65 to 80°C. It is also shown that the CrCr complex [CpCr(CO)2]2 reacted with [(iPrO)2P(S)S]2, albeit much less readily, generating 3 as the eventual product.

AB - The facile reaction of [CpCr(CO)3]2 (Cp=η5-C5H5) with one mole equivalent of bis(thiophosphoryl)disulfanes, (RO)2P(S)SSP(S)(OR)2 (R=iPr), at ambient temperature, led to the isolation of dark-purple solids of CpCr(CO)2(S2P(OR)2) (2, yield: 32%) and blue solids of CpCr(S2P(OR)2)2 (3, yield: 30%). At 70-80°C, the reaction gave 3 (yield: 35%) and Cr(S2P(OR)2)3 (4, yield: 11%). 1H-NMR spectral studies demonstrated that 3 and 4 were derived from 2, the primary product. X-ray diffraction analyses showed that 2 possesses cis CO ligands and a bidentate SP(S)(OR)2 ligand, while 3 contains both an unidentate and a bidentate ligand, and in 4 the Cr atom is octahedrally symmetrically coordinated to the three bidentate phosphorylthioato ligand. Variable temperature 1H and 31P spectral studies showed the occurrence of very rapid unidentate-bidentate exchange between the ligands in 3 in the temperature range -65 to 80°C. It is also shown that the CrCr complex [CpCr(CO)2]2 reacted with [(iPrO)2P(S)S]2, albeit much less readily, generating 3 as the eventual product.

KW - 15-Electron chromium(III)

KW - Crystal structures

KW - Cyclopentadienylchromium

KW - Di-isopropyldithiophosphate

KW - Phosphorodithioato

UR - http://www.scopus.com/inward/record.url?scp=0010970499&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0010970499&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(01)01031-2

DO - 10.1016/S0022-328X(01)01031-2

M3 - Article

AN - SCOPUS:0010970499

SN - 0022-328X

VL - 631

SP - 67

EP - 75

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -