Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] and [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]

Philip J. Blower; Jonathan R. Dilworth; John Hutchinson; Terry Nicholson; Jon A. Zubieta

doi:10.1039/DT9850002639

Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH₄][Mo(SC₆H₂Prⁱ ₃-2,4,6)₃(CO)₂] and [Mo(NNPh)(SC₆H₂Prⁱ₃-2,4,6) ₃(NCMe)]

Philip J. Blower, Jonathan R. Dilworth, John Hutchinson, Terry Nicholson, Jon A. Zubieta

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

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Abstract

[MBr₂(CO)₄] (M = MO or W) react with thiolate anions SR^- to give the anions [M(SR)₃(CO)₂]^-(SR = SC₆H₂Prⁱ₃-2,4,6, SC₆H₃Prⁱ₂-2,6, SC₆H₂Br-4-Prⁱ₂-2,6, SC₆H₂Me₃-2,4,6, SC₆F₅). The complex [PPh₄][Mo(SC₆H₂Prⁱ ₃-2,4,6)₃(CO)₂] crystallises in space group P1 with a = 13.451 (2), b = 14.229(2), c = 19.862(3) Å, α = 96.11(1), β = 94.11(1), γ = 111.04(1)°, and Z = 2. Structure analysis based on 2 939 reflections with I_o < 3.0σ(I_o) refined to R = 0.0755. The anion has a trigonal-bipyramidal structure with axial co-ligands. The complexes [M(SR)₃(CO)₂]^- react with CO to give [M(SR)₃(CO)₃]^-. [Mo(SC₆H₂Prⁱ₃-2,4,6) ₃(CO)₂]^- reacts with neutral donors L to give [Mo(SC₆H₂Prⁱ₃-2,4,6) ₃(CO)L]^- (L = MeCN, Bu^tCN, PMe₂Ph, or Bu^tNC) and with [N₂Ph][BF₄] in MeCN to give [Mo(NNPh)(SC₆H₂Prⁱ₃-2,4,6) ₃(NCMe)]. This complex crystallises in space group Pnma with a = 9.962(3), b = 21.002(4), c = 27.646(4) Å, and Z = 4. Structure analysis based on 1 772 reflections with I_o > 3σ(I_o) refined to R = 0.075. The NNPh and MeCN ligands occupy the axial sites of a trigonal bipyramid with the thiolates equatorial.

Original language	English (US)
Pages (from-to)	2639-2645
Number of pages	7
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	12
DOIs	https://doi.org/10.1039/DT9850002639
State	Published - 1985
Externally published	Yes

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General Chemistry

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Blower, P. J., Dilworth, J. R., Hutchinson, J., Nicholson, T., & Zubieta, J. A. (1985). Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH₄][Mo(SC₆H₂Prⁱ ₃-2,4,6)₃(CO)₂] and [Mo(NNPh)(SC₆H₂Prⁱ₃-2,4,6) ₃(NCMe)]. Journal of the Chemical Society, Dalton Transactions, (12), 2639-2645. https://doi.org/10.1039/DT9850002639

Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH₄][Mo(SC₆H₂Prⁱ ₃-2,4,6)₃(CO)₂] and [Mo(NNPh)(SC₆H₂Prⁱ₃-2,4,6) ₃(NCMe)]. / Blower, Philip J.; Dilworth, Jonathan R.; Hutchinson, John et al.
In: Journal of the Chemical Society, Dalton Transactions, No. 12, 1985, p. 2639-2645.

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

Blower, PJ, Dilworth, JR, Hutchinson, J, Nicholson, T & Zubieta, JA 1985, 'Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH₄][Mo(SC₆H₂Prⁱ ₃-2,4,6)₃(CO)₂] and [Mo(NNPh)(SC₆H₂Prⁱ₃-2,4,6) ₃(NCMe)]', Journal of the Chemical Society, Dalton Transactions, no. 12, pp. 2639-2645. https://doi.org/10.1039/DT9850002639

Blower PJ, Dilworth JR, Hutchinson J, Nicholson T, Zubieta JA. Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH₄][Mo(SC₆H₂Prⁱ ₃-2,4,6)₃(CO)₂] and [Mo(NNPh)(SC₆H₂Prⁱ₃-2,4,6) ₃(NCMe)]. Journal of the Chemical Society, Dalton Transactions. 1985;(12):2639-2645. doi: 10.1039/DT9850002639

Blower, Philip J. ; Dilworth, Jonathan R. ; Hutchinson, John et al. / Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH₄][Mo(SC₆H₂Prⁱ ₃-2,4,6)₃(CO)₂] and [Mo(NNPh)(SC₆H₂Prⁱ₃-2,4,6) ₃(NCMe)]. In: Journal of the Chemical Society, Dalton Transactions. 1985 ; No. 12. pp. 2639-2645.

@article{a5702e9773e849e68c947955a6ccac7b,

title = "Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] and [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]",

abstract = "[MBr2(CO)4] (M = MO or W) react with thiolate anions SR- to give the anions [M(SR)3(CO)2]-(SR = SC6H2Pri3-2,4,6, SC6H3Pri2-2,6, SC6H2Br-4-Pri2-2,6, SC6H2Me3-2,4,6, SC6F5). The complex [PPh4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] crystallises in space group P1 with a = 13.451 (2), b = 14.229(2), c = 19.862(3) {\AA}, α = 96.11(1), β = 94.11(1), γ = 111.04(1)°, and Z = 2. Structure analysis based on 2 939 reflections with Io < 3.0σ(Io) refined to R = 0.0755. The anion has a trigonal-bipyramidal structure with axial co-ligands. The complexes [M(SR)3(CO)2]- react with CO to give [M(SR)3(CO)3]-. [Mo(SC6H2Pri3-2,4,6) 3(CO)2]- reacts with neutral donors L to give [Mo(SC6H2Pri3-2,4,6) 3(CO)L]- (L = MeCN, ButCN, PMe2Ph, or ButNC) and with [N2Ph][BF4] in MeCN to give [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]. This complex crystallises in space group Pnma with a = 9.962(3), b = 21.002(4), c = 27.646(4) {\AA}, and Z = 4. Structure analysis based on 1 772 reflections with Io > 3σ(Io) refined to R = 0.075. The NNPh and MeCN ligands occupy the axial sites of a trigonal bipyramid with the thiolates equatorial.",

author = "Blower, {Philip J.} and Dilworth, {Jonathan R.} and John Hutchinson and Terry Nicholson and Zubieta, {Jon A.}",

year = "1985",

doi = "10.1039/DT9850002639",

language = "English (US)",

pages = "2639--2645",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "12",

}

TY - JOUR

T1 - Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] and [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]

AU - Blower, Philip J.

AU - Dilworth, Jonathan R.

AU - Hutchinson, John

AU - Nicholson, Terry

AU - Zubieta, Jon A.

PY - 1985

Y1 - 1985

N2 - [MBr2(CO)4] (M = MO or W) react with thiolate anions SR- to give the anions [M(SR)3(CO)2]-(SR = SC6H2Pri3-2,4,6, SC6H3Pri2-2,6, SC6H2Br-4-Pri2-2,6, SC6H2Me3-2,4,6, SC6F5). The complex [PPh4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] crystallises in space group P1 with a = 13.451 (2), b = 14.229(2), c = 19.862(3) Å, α = 96.11(1), β = 94.11(1), γ = 111.04(1)°, and Z = 2. Structure analysis based on 2 939 reflections with Io < 3.0σ(Io) refined to R = 0.0755. The anion has a trigonal-bipyramidal structure with axial co-ligands. The complexes [M(SR)3(CO)2]- react with CO to give [M(SR)3(CO)3]-. [Mo(SC6H2Pri3-2,4,6) 3(CO)2]- reacts with neutral donors L to give [Mo(SC6H2Pri3-2,4,6) 3(CO)L]- (L = MeCN, ButCN, PMe2Ph, or ButNC) and with [N2Ph][BF4] in MeCN to give [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]. This complex crystallises in space group Pnma with a = 9.962(3), b = 21.002(4), c = 27.646(4) Å, and Z = 4. Structure analysis based on 1 772 reflections with Io > 3σ(Io) refined to R = 0.075. The NNPh and MeCN ligands occupy the axial sites of a trigonal bipyramid with the thiolates equatorial.

AB - [MBr2(CO)4] (M = MO or W) react with thiolate anions SR- to give the anions [M(SR)3(CO)2]-(SR = SC6H2Pri3-2,4,6, SC6H3Pri2-2,6, SC6H2Br-4-Pri2-2,6, SC6H2Me3-2,4,6, SC6F5). The complex [PPh4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] crystallises in space group P1 with a = 13.451 (2), b = 14.229(2), c = 19.862(3) Å, α = 96.11(1), β = 94.11(1), γ = 111.04(1)°, and Z = 2. Structure analysis based on 2 939 reflections with Io < 3.0σ(Io) refined to R = 0.0755. The anion has a trigonal-bipyramidal structure with axial co-ligands. The complexes [M(SR)3(CO)2]- react with CO to give [M(SR)3(CO)3]-. [Mo(SC6H2Pri3-2,4,6) 3(CO)2]- reacts with neutral donors L to give [Mo(SC6H2Pri3-2,4,6) 3(CO)L]- (L = MeCN, ButCN, PMe2Ph, or ButNC) and with [N2Ph][BF4] in MeCN to give [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]. This complex crystallises in space group Pnma with a = 9.962(3), b = 21.002(4), c = 27.646(4) Å, and Z = 4. Structure analysis based on 1 772 reflections with Io > 3σ(Io) refined to R = 0.075. The NNPh and MeCN ligands occupy the axial sites of a trigonal bipyramid with the thiolates equatorial.

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