Complexes from ring opening of Lawesson's Reagent and phosphorus-phosphorus coupling

Zhiqiang Weng; Weng Kee Leong; Jagadese J. Vittal; Lai Yoong Goh

doi:10.1021/om020933z

Complexes from ring opening of Lawesson's Reagent and phosphorus-phosphorus coupling

Zhiqiang Weng, Weng Kee Leong, Jagadese J. Vittal, Lai Yoong Goh^*

^*Corresponding author for this work

National University of Singapore

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

23 Citations (Scopus)

Abstract

At ambient temperature the reaction of [CpCr(CO)₃]₂ (1; Cp = η⁵-C₅H₅) with 1 mol equiv of Lawesson's reagent, Ar₂P₂S₄ (2; Ar = C₆H₄OCH₃), for 3 h led to the isolation of brown crystals of Cp₂Cr₂(CO)₅(SPAr) (3), dark red solids of Cp₂Cr₂(CO)₅(S₂PAr) (4), deep blue solids of Cp₂Cr₂(S₂P(O)Ar)₂ (5), greenish yellow solids of CpCr(CO)₃H (9), and deep green crystals of Cp₂Cr₂(CO)₄S (10) with yields of 5, 11, 20, 7, and 8%, respectively; a similar reaction at 90°C for 2 h gave 5 (36%), CpCr(CO)₂(SP(H)Ar) (6) as red crystals (9%), [CpCr(CO)₂(SPAr)]₂ (cis-7) as dark brown crystalline solids (14%), and its isomer trans-7 as dark red crystals (5%), together with 9 (4%) and 10 (11%). The ambient-temperature reaction of [Cp*Cr(CO)₃]₂ (1*; Cp* = η⁵-C₅Me₅) yielded the Cp* analogues of 4, 5, 9, and 10, i.e., 4*, 5*, 9*, and 10* with yields of 51, 17, 6, and 8%, respectively. The thermolysis of Cp*₂Cr₂(CO)₅(S₂PAr) (4*) resulted in the isolation of Cp*Cr(CO)₂(SP(H)Ar) (6*), Cp*₂Cr₂(CO)₄(SPAr) (8*), and Cp*₂-Cr₂(S₂P(O)Ar)₂ (5*) with yields of 7, 14, and 13%, respectively. A NMR spectral study demonstrated that thermolytic degradation of complex 3 or its reaction with sulfur or Lawesson's reagent (2) led to the formation of cis-7; cis- and trans-7 were found to interconvert under elevated temperatures, giving 4:1 equilibrium mixtures at 80°C both isomers react with 1 to re-form 3. The solid-state structures of all the above-mentioned complexes have been characterized by single-crystal X-ray diffraction analysis. Complexes 3 and 8* contain the phosphinothioylidene ligand in different coordination modes. The analogous structures of complexes 4/4* reveal a bridging dithiophosphorane ligand, being η²(S,S′) coordinated to a Cp/Cp*Cr(CO)₂ moiety and η¹(P) coordinated to a Cp/Cp*Cr(CO)₃ moiety. The similar molecular structures of 5 and 5* contain an eight-membered ring, comprising two CpCr/ Cp*Cr units and two [S₂P(O)Ar] moieties. Complexes 6/6* contain a rare η²-arylthioxophosphane ligand. The complexes cis- and trans-7 are conformers of a P-P-bonded dimer.

Original language	English
Pages (from-to)	1645-1656
Number of pages	12
Journal	Organometallics
Volume	22
Issue number	8
DOIs	https://doi.org/10.1021/om020933z
Publication status	Published - Apr 14 2003
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{ca2b71ad49c94b9eaf8d01cfab51d399,

title = "Complexes from ring opening of Lawesson's Reagent and phosphorus-phosphorus coupling",

abstract = "At ambient temperature the reaction of [CpCr(CO)3]2 (1; Cp = η5-C5H5) with 1 mol equiv of Lawesson's reagent, Ar2P2S4 (2; Ar = C6H4OCH3), for 3 h led to the isolation of brown crystals of Cp2Cr2(CO)5(SPAr) (3), dark red solids of Cp2Cr2(CO)5(S2PAr) (4), deep blue solids of Cp2Cr2(S2P(O)Ar)2 (5), greenish yellow solids of CpCr(CO)3H (9), and deep green crystals of Cp2Cr2(CO)4S (10) with yields of 5, 11, 20, 7, and 8%, respectively; a similar reaction at 90°C for 2 h gave 5 (36%), CpCr(CO)2(SP(H)Ar) (6) as red crystals (9%), [CpCr(CO)2(SPAr)]2 (cis-7) as dark brown crystalline solids (14%), and its isomer trans-7 as dark red crystals (5%), together with 9 (4%) and 10 (11%). The ambient-temperature reaction of [Cp*Cr(CO)3]2 (1*; Cp* = η5-C5Me5) yielded the Cp* analogues of 4, 5, 9, and 10, i.e., 4*, 5*, 9*, and 10* with yields of 51, 17, 6, and 8%, respectively. The thermolysis of Cp*2Cr2(CO)5(S2PAr) (4*) resulted in the isolation of Cp*Cr(CO)2(SP(H)Ar) (6*), Cp*2Cr2(CO)4(SPAr) (8*), and Cp*2-Cr2(S2P(O)Ar)2 (5*) with yields of 7, 14, and 13%, respectively. A NMR spectral study demonstrated that thermolytic degradation of complex 3 or its reaction with sulfur or Lawesson's reagent (2) led to the formation of cis-7; cis- and trans-7 were found to interconvert under elevated temperatures, giving 4:1 equilibrium mixtures at 80°C both isomers react with 1 to re-form 3. The solid-state structures of all the above-mentioned complexes have been characterized by single-crystal X-ray diffraction analysis. Complexes 3 and 8* contain the phosphinothioylidene ligand in different coordination modes. The analogous structures of complexes 4/4* reveal a bridging dithiophosphorane ligand, being η2(S,S′) coordinated to a Cp/Cp*Cr(CO)2 moiety and η1(P) coordinated to a Cp/Cp*Cr(CO)3 moiety. The similar molecular structures of 5 and 5* contain an eight-membered ring, comprising two CpCr/ Cp*Cr units and two [S2P(O)Ar] moieties. Complexes 6/6* contain a rare η2-arylthioxophosphane ligand. The complexes cis- and trans-7 are conformers of a P-P-bonded dimer.",

author = "Zhiqiang Weng and Leong, {Weng Kee} and Vittal, {Jagadese J.} and Goh, {Lai Yoong}",

year = "2003",

month = apr,

day = "14",

doi = "10.1021/om020933z",

language = "English",

volume = "22",

pages = "1645--1656",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Complexes from ring opening of Lawesson's Reagent and phosphorus-phosphorus coupling

AU - Weng, Zhiqiang

AU - Leong, Weng Kee

AU - Vittal, Jagadese J.

AU - Goh, Lai Yoong

PY - 2003/4/14

Y1 - 2003/4/14

N2 - At ambient temperature the reaction of [CpCr(CO)3]2 (1; Cp = η5-C5H5) with 1 mol equiv of Lawesson's reagent, Ar2P2S4 (2; Ar = C6H4OCH3), for 3 h led to the isolation of brown crystals of Cp2Cr2(CO)5(SPAr) (3), dark red solids of Cp2Cr2(CO)5(S2PAr) (4), deep blue solids of Cp2Cr2(S2P(O)Ar)2 (5), greenish yellow solids of CpCr(CO)3H (9), and deep green crystals of Cp2Cr2(CO)4S (10) with yields of 5, 11, 20, 7, and 8%, respectively; a similar reaction at 90°C for 2 h gave 5 (36%), CpCr(CO)2(SP(H)Ar) (6) as red crystals (9%), [CpCr(CO)2(SPAr)]2 (cis-7) as dark brown crystalline solids (14%), and its isomer trans-7 as dark red crystals (5%), together with 9 (4%) and 10 (11%). The ambient-temperature reaction of [Cp*Cr(CO)3]2 (1*; Cp* = η5-C5Me5) yielded the Cp* analogues of 4, 5, 9, and 10, i.e., 4*, 5*, 9*, and 10* with yields of 51, 17, 6, and 8%, respectively. The thermolysis of Cp*2Cr2(CO)5(S2PAr) (4*) resulted in the isolation of Cp*Cr(CO)2(SP(H)Ar) (6*), Cp*2Cr2(CO)4(SPAr) (8*), and Cp*2-Cr2(S2P(O)Ar)2 (5*) with yields of 7, 14, and 13%, respectively. A NMR spectral study demonstrated that thermolytic degradation of complex 3 or its reaction with sulfur or Lawesson's reagent (2) led to the formation of cis-7; cis- and trans-7 were found to interconvert under elevated temperatures, giving 4:1 equilibrium mixtures at 80°C both isomers react with 1 to re-form 3. The solid-state structures of all the above-mentioned complexes have been characterized by single-crystal X-ray diffraction analysis. Complexes 3 and 8* contain the phosphinothioylidene ligand in different coordination modes. The analogous structures of complexes 4/4* reveal a bridging dithiophosphorane ligand, being η2(S,S′) coordinated to a Cp/Cp*Cr(CO)2 moiety and η1(P) coordinated to a Cp/Cp*Cr(CO)3 moiety. The similar molecular structures of 5 and 5* contain an eight-membered ring, comprising two CpCr/ Cp*Cr units and two [S2P(O)Ar] moieties. Complexes 6/6* contain a rare η2-arylthioxophosphane ligand. The complexes cis- and trans-7 are conformers of a P-P-bonded dimer.

AB - At ambient temperature the reaction of [CpCr(CO)3]2 (1; Cp = η5-C5H5) with 1 mol equiv of Lawesson's reagent, Ar2P2S4 (2; Ar = C6H4OCH3), for 3 h led to the isolation of brown crystals of Cp2Cr2(CO)5(SPAr) (3), dark red solids of Cp2Cr2(CO)5(S2PAr) (4), deep blue solids of Cp2Cr2(S2P(O)Ar)2 (5), greenish yellow solids of CpCr(CO)3H (9), and deep green crystals of Cp2Cr2(CO)4S (10) with yields of 5, 11, 20, 7, and 8%, respectively; a similar reaction at 90°C for 2 h gave 5 (36%), CpCr(CO)2(SP(H)Ar) (6) as red crystals (9%), [CpCr(CO)2(SPAr)]2 (cis-7) as dark brown crystalline solids (14%), and its isomer trans-7 as dark red crystals (5%), together with 9 (4%) and 10 (11%). The ambient-temperature reaction of [Cp*Cr(CO)3]2 (1*; Cp* = η5-C5Me5) yielded the Cp* analogues of 4, 5, 9, and 10, i.e., 4*, 5*, 9*, and 10* with yields of 51, 17, 6, and 8%, respectively. The thermolysis of Cp*2Cr2(CO)5(S2PAr) (4*) resulted in the isolation of Cp*Cr(CO)2(SP(H)Ar) (6*), Cp*2Cr2(CO)4(SPAr) (8*), and Cp*2-Cr2(S2P(O)Ar)2 (5*) with yields of 7, 14, and 13%, respectively. A NMR spectral study demonstrated that thermolytic degradation of complex 3 or its reaction with sulfur or Lawesson's reagent (2) led to the formation of cis-7; cis- and trans-7 were found to interconvert under elevated temperatures, giving 4:1 equilibrium mixtures at 80°C both isomers react with 1 to re-form 3. The solid-state structures of all the above-mentioned complexes have been characterized by single-crystal X-ray diffraction analysis. Complexes 3 and 8* contain the phosphinothioylidene ligand in different coordination modes. The analogous structures of complexes 4/4* reveal a bridging dithiophosphorane ligand, being η2(S,S′) coordinated to a Cp/Cp*Cr(CO)2 moiety and η1(P) coordinated to a Cp/Cp*Cr(CO)3 moiety. The similar molecular structures of 5 and 5* contain an eight-membered ring, comprising two CpCr/ Cp*Cr units and two [S2P(O)Ar] moieties. Complexes 6/6* contain a rare η2-arylthioxophosphane ligand. The complexes cis- and trans-7 are conformers of a P-P-bonded dimer.

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Complexes from ring opening of Lawesson's Reagent and phosphorus-phosphorus coupling

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