Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls: Molecular structure of [Mo(CO)2(NO){HB(3,5-Me2-4-PhCH2C 3N2)3}], a complex with an 'inverted' bowl-like structure

John C. Jeffery; Stefan S. Kurek; Jon A. McCleverty; Elefteria Psillakis; Rob M. Richardson; Michael D. Ward; Andrzej Wlodarczyk

doi:10.1039/DT9940002559

Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls: Molecular structure of [Mo(CO)₂(NO){HB(3,5-Me₂-4-PhCH₂C ₃N₂)₃}], a complex with an 'inverted' bowl-like structure

John C. Jeffery, Stefan S. Kurek, Jon A. McCleverty^*, Elefteria Psillakis, Rob M. Richardson, Michael D. Ward, Andrzej Wlodarczyk

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

24 Citations (Scopus)

Abstract

Reaction of [HB(bdmpz)₃]^-, obtained by reaction of 4-benzyl-3,5-dimethylpyrazole (Hbdmpz) with KBH₄, with [M(CO)₆] (M = Mo or W) and p-MeC₆H₄SO₂N(NO)Me afforded [M(CO)₂(NO)-{HB(bdmpz)₃}] (M = Mo or W). The molybdenum carbonyl was converted into [Mo(NO)-{HB(bdmpz)₃}X(Y)] (X = Y = Cl, I or OC₆H₄Me-p; X = Cl, Y = OMe or OC₆H₄Me-p) the spectral and electrochemical properties of which are virtually identical to those of [Mo(NO){HB(dmpz)₃}X(Y)] (Hdmpz = 3,5-dimethylpyrazole), indicating that the addition of a benzyl group has no significant electronic effect in the new species. However, a crystal and molecular structure determination of [Mo(CO)₂(NO){HB(bdmpz)₃}] revealed that the molecule has a highly symmetrical structure, the CH₂ groups of the benzyl groups in the tris(pyrazolyl)borate ligand being disposed in a star-shaped configuration where the phenyl rings adopt an 'inverted' bowl-like structure with the BH group inside and the Mo(CO)₂(NO) group outside the bowl. The arrangement of the 4-benzyl groups with respect to the pyrazolyl rings and the H-B ⋯ Mo three-fold axis is strongly reminiscent of an inverted three-legged 'Isle of Man' symbol.

Original language	English
Pages (from-to)	2559-2564
Number of pages	6
Journal	Journal of the Chemical Society: Dalton Transactions
Issue number	17
DOIs	https://doi.org/10.1039/DT9940002559
Publication status	Published - 1 Dec 1994

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Jeffery, J. C., Kurek, S. S., McCleverty, J. A., Psillakis, E., Richardson, R. M., Ward, M. D., & Wlodarczyk, A. (1994). Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls: Molecular structure of [Mo(CO)₂(NO){HB(3,5-Me₂-4-PhCH₂C ₃N₂)₃}], a complex with an 'inverted' bowl-like structure. Journal of the Chemical Society: Dalton Transactions, (17), 2559-2564. https://doi.org/10.1039/DT9940002559

@article{691b2a604be84c0486d2d9b08443c815,

title = "Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls: Molecular structure of [Mo(CO)2(NO)\{HB(3,5-Me2-4-PhCH2C 3N2)3\}], a complex with an 'inverted' bowl-like structure",

abstract = "Reaction of [HB(bdmpz)3]-, obtained by reaction of 4-benzyl-3,5-dimethylpyrazole (Hbdmpz) with KBH4, with [M(CO)6] (M = Mo or W) and p-MeC6H4SO2N(NO)Me afforded [M(CO)2(NO)-\{HB(bdmpz)3\}] (M = Mo or W). The molybdenum carbonyl was converted into [Mo(NO)-\{HB(bdmpz)3\}X(Y)] (X = Y = Cl, I or OC6H4Me-p; X = Cl, Y = OMe or OC6H4Me-p) the spectral and electrochemical properties of which are virtually identical to those of [Mo(NO)\{HB(dmpz)3\}X(Y)] (Hdmpz = 3,5-dimethylpyrazole), indicating that the addition of a benzyl group has no significant electronic effect in the new species. However, a crystal and molecular structure determination of [Mo(CO)2(NO)\{HB(bdmpz)3\}] revealed that the molecule has a highly symmetrical structure, the CH2 groups of the benzyl groups in the tris(pyrazolyl)borate ligand being disposed in a star-shaped configuration where the phenyl rings adopt an 'inverted' bowl-like structure with the BH group inside and the Mo(CO)2(NO) group outside the bowl. The arrangement of the 4-benzyl groups with respect to the pyrazolyl rings and the H-B ⋯ Mo three-fold axis is strongly reminiscent of an inverted three-legged 'Isle of Man' symbol.",

author = "Jeffery, \{John C.\} and Kurek, \{Stefan S.\} and McCleverty, \{Jon A.\} and Elefteria Psillakis and Richardson, \{Rob M.\} and Ward, \{Michael D.\} and Andrzej Wlodarczyk",

year = "1994",

month = dec,

day = "1",

doi = "10.1039/DT9940002559",

language = "English",

pages = "2559--2564",

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

issn = "0300-9246",

publisher = "Royal Society of Chemistry",

number = "17",

}

Jeffery, JC, Kurek, SS, McCleverty, JA, Psillakis, E, Richardson, RM, Ward, MD & Wlodarczyk, A 1994, 'Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls: Molecular structure of [Mo(CO)₂(NO){HB(3,5-Me₂-4-PhCH₂C ₃N₂)₃}], a complex with an 'inverted' bowl-like structure', Journal of the Chemical Society: Dalton Transactions, no. 17, pp. 2559-2564. https://doi.org/10.1039/DT9940002559

Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls: Molecular structure of [Mo(CO)₂(NO){HB(3,5-Me₂-4-PhCH₂C ₃N₂)₃}], a complex with an 'inverted' bowl-like structure. / Jeffery, John C.; Kurek, Stefan S.; McCleverty, Jon A. et al.
In: Journal of the Chemical Society: Dalton Transactions, No. 17, 01.12.1994, p. 2559-2564.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

TY - JOUR

T1 - Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls

T2 - Molecular structure of [Mo(CO)2(NO){HB(3,5-Me2-4-PhCH2C 3N2)3}], a complex with an 'inverted' bowl-like structure

AU - Jeffery, John C.

AU - Kurek, Stefan S.

AU - McCleverty, Jon A.

AU - Psillakis, Elefteria

AU - Richardson, Rob M.

AU - Ward, Michael D.

AU - Wlodarczyk, Andrzej

PY - 1994/12/1

Y1 - 1994/12/1

N2 - Reaction of [HB(bdmpz)3]-, obtained by reaction of 4-benzyl-3,5-dimethylpyrazole (Hbdmpz) with KBH4, with [M(CO)6] (M = Mo or W) and p-MeC6H4SO2N(NO)Me afforded [M(CO)2(NO)-{HB(bdmpz)3}] (M = Mo or W). The molybdenum carbonyl was converted into [Mo(NO)-{HB(bdmpz)3}X(Y)] (X = Y = Cl, I or OC6H4Me-p; X = Cl, Y = OMe or OC6H4Me-p) the spectral and electrochemical properties of which are virtually identical to those of [Mo(NO){HB(dmpz)3}X(Y)] (Hdmpz = 3,5-dimethylpyrazole), indicating that the addition of a benzyl group has no significant electronic effect in the new species. However, a crystal and molecular structure determination of [Mo(CO)2(NO){HB(bdmpz)3}] revealed that the molecule has a highly symmetrical structure, the CH2 groups of the benzyl groups in the tris(pyrazolyl)borate ligand being disposed in a star-shaped configuration where the phenyl rings adopt an 'inverted' bowl-like structure with the BH group inside and the Mo(CO)2(NO) group outside the bowl. The arrangement of the 4-benzyl groups with respect to the pyrazolyl rings and the H-B ⋯ Mo three-fold axis is strongly reminiscent of an inverted three-legged 'Isle of Man' symbol.

AB - Reaction of [HB(bdmpz)3]-, obtained by reaction of 4-benzyl-3,5-dimethylpyrazole (Hbdmpz) with KBH4, with [M(CO)6] (M = Mo or W) and p-MeC6H4SO2N(NO)Me afforded [M(CO)2(NO)-{HB(bdmpz)3}] (M = Mo or W). The molybdenum carbonyl was converted into [Mo(NO)-{HB(bdmpz)3}X(Y)] (X = Y = Cl, I or OC6H4Me-p; X = Cl, Y = OMe or OC6H4Me-p) the spectral and electrochemical properties of which are virtually identical to those of [Mo(NO){HB(dmpz)3}X(Y)] (Hdmpz = 3,5-dimethylpyrazole), indicating that the addition of a benzyl group has no significant electronic effect in the new species. However, a crystal and molecular structure determination of [Mo(CO)2(NO){HB(bdmpz)3}] revealed that the molecule has a highly symmetrical structure, the CH2 groups of the benzyl groups in the tris(pyrazolyl)borate ligand being disposed in a star-shaped configuration where the phenyl rings adopt an 'inverted' bowl-like structure with the BH group inside and the Mo(CO)2(NO) group outside the bowl. The arrangement of the 4-benzyl groups with respect to the pyrazolyl rings and the H-B ⋯ Mo three-fold axis is strongly reminiscent of an inverted three-legged 'Isle of Man' symbol.

UR - https://www.scopus.com/pages/publications/37049088826

U2 - 10.1039/DT9940002559

DO - 10.1039/DT9940002559

M3 - Article (Academic Journal)

AN - SCOPUS:37049088826

SN - 0300-9246

SP - 2559

EP - 2564

JO - Journal of the Chemical Society: Dalton Transactions

JF - Journal of the Chemical Society: Dalton Transactions

IS - 17

ER -

Jeffery JC, Kurek SS, McCleverty JA, Psillakis E, Richardson RM, Ward MD et al. Syntheses of 4-benzyl-3,5-dimethylpyrazolylborato complexes of molybdenum and tungsten nitrosyls: Molecular structure of [Mo(CO)₂(NO){HB(3,5-Me₂-4-PhCH₂C ₃N₂)₃}], a complex with an 'inverted' bowl-like structure. Journal of the Chemical Society: Dalton Transactions. 1994 Dec 1;(17):2559-2564. doi: 10.1039/DT9940002559