Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S2CNEt2)2(Ph2PCH2CH2PPh2)][BF4] and [MoCl(S2CNEt2)2(PPh2Me)2][PF6] and the Mechanism of Their Electrochemical Reduction

Jonathan R. Dilworth; Bryan D. Neaves; Christopher J. Pickett; Joseph Chatt; Jon A. Zubieta

doi:10.1021/ic00166a009

Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S₂CNEt₂)₂(Ph₂PCH₂CH₂PPh₂)][BF₄] and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂][PF₆] and the Mechanism of Their Electrochemical Reduction

Jonathan R. Dilworth, Bryan D. Neaves, Christopher J. Pickett, Joseph Chatt, Jon A. Zubieta

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

23 Scopus citations

Abstract

The complexes [MoX(S₂CNR₂)₂P₂] [Y] or [MoX₂(S₂CNR₂)₂P] (R₂ = Me₂, Et₂, or (CH₂)₅; X = CI or Br; Y = Cl, PF₆, BF₄, or BPh₄; P = 1/2 Ph₂PCH₂CH₂PPh₂, PPh₂Me, PMe₂Ph, or PEt₂Ph) are prepared from [MoOX₂(S₂CNR₂)₂] and P. The crystal and molecular structures of [MoCl(S₂CNEt₂)₂(dppe)] [BF₄] (I) and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂] [PF₆] (VII) have been determined by single-crystal X-ray diffraction methods. Crystal data for complex I: space group P1, a = 11.422 (7) Å, b = 11.902 (9) Å, c = 16.900 (8) Å, α = 104.64 (l)°,β = 101.65 (2)°, γ = 103.34 (1)°, V= 2078.60 Å3, Z = 2, R = 6.8% from 5429 reflections. Crystal data for complex VII: space group P2'2'2’, a = 9.132 (7) Å, b = 17.028 (7)Å, c = 28.084 (7) Å,V= 4367.42 Å³, Z = 4, R = 9.8% from 2783 reflections. Both complexes have distorted pentagonal-bipyramidal geometries. Chemical or electrochemical reduction of [MoCl(S₂CNR₂)₂(dppe)]⁺ under CO gives [Mo(CO)(S₂CNR₂)₂(dppe)], whereas under N₂ or Ar dimeric [{Mo(S₂CNR₂)₂(dppe)}₂]²⁺ is formed. The redox chemistry of these species and other intermediates has been studied by a range of electrochemical techniques, and reduction mechanisms are proposed, together with the implications for the binding of small molecules to the reductively generated site.

Original language	English (US)
Pages (from-to)	3524-3529
Number of pages	6
Journal	Inorganic Chemistry
Volume	22
Issue number	24
DOIs	https://doi.org/10.1021/ic00166a009
State	Published - Nov 1983
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic00166a009

Fingerprint

Dive into the research topics of 'Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S₂CNEt₂)₂(Ph₂PCH₂CH₂PPh₂)][BF₄] and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂][PF₆] and the Mechanism of Their Electrochemical Reduction'. Together they form a unique fingerprint.

Cite this

Dilworth, J. R., Neaves, B. D., Pickett, C. J., Chatt, J., & Zubieta, J. A. (1983). Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S₂CNEt₂)₂(Ph₂PCH₂CH₂PPh₂)][BF₄] and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂][PF₆] and the Mechanism of Their Electrochemical Reduction. Inorganic Chemistry, 22(24), 3524-3529. https://doi.org/10.1021/ic00166a009

Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S₂CNEt₂)₂(Ph₂PCH₂CH₂PPh₂)][BF₄] and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂][PF₆] and the Mechanism of Their Electrochemical Reduction. / Dilworth, Jonathan R.; Neaves, Bryan D.; Pickett, Christopher J. et al.
In: Inorganic Chemistry, Vol. 22, No. 24, 11.1983, p. 3524-3529.

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

Dilworth, JR, Neaves, BD, Pickett, CJ, Chatt, J & Zubieta, JA 1983, 'Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S₂CNEt₂)₂(Ph₂PCH₂CH₂PPh₂)][BF₄] and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂][PF₆] and the Mechanism of Their Electrochemical Reduction', Inorganic Chemistry, vol. 22, no. 24, pp. 3524-3529. https://doi.org/10.1021/ic00166a009

Dilworth JR, Neaves BD, Pickett CJ, Chatt J, Zubieta JA. Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S₂CNEt₂)₂(Ph₂PCH₂CH₂PPh₂)][BF₄] and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂][PF₆] and the Mechanism of Their Electrochemical Reduction. Inorganic Chemistry. 1983 Nov;22(24):3524-3529. doi: 10.1021/ic00166a009

Dilworth, Jonathan R. ; Neaves, Bryan D. ; Pickett, Christopher J. et al. / Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S₂CNEt₂)₂(Ph₂PCH₂CH₂PPh₂)][BF₄] and [MoCl(S₂CNEt₂)₂(PPh₂Me)₂][PF₆] and the Mechanism of Their Electrochemical Reduction. In: Inorganic Chemistry. 1983 ; Vol. 22, No. 24. pp. 3524-3529.

@article{d9c6ec72ee1d461ba97b54ac712cf8db,

title = "Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S2CNEt2)2(Ph2PCH2CH2PPh2)][BF4] and [MoCl(S2CNEt2)2(PPh2Me)2][PF6] and the Mechanism of Their Electrochemical Reduction",

abstract = "The complexes [MoX(S2CNR2)2P2] [Y] or [MoX2(S2CNR2)2P] (R2 = Me2, Et2, or (CH2)5; X = CI or Br; Y = Cl, PF6, BF4, or BPh4; P = 1/2 Ph2PCH2CH2PPh2, PPh2Me, PMe2Ph, or PEt2Ph) are prepared from [MoOX2(S2CNR2)2] and P. The crystal and molecular structures of [MoCl(S2CNEt2)2(dppe)] [BF4] (I) and [MoCl(S2CNEt2)2(PPh2Me)2] [PF6] (VII) have been determined by single-crystal X-ray diffraction methods. Crystal data for complex I: space group P1, a = 11.422 (7) {\AA}, b = 11.902 (9) {\AA}, c = 16.900 (8) {\AA}, α = 104.64 (l)°,β = 101.65 (2)°, γ = 103.34 (1)°, V= 2078.60 {\AA}3, Z = 2, R = 6.8% from 5429 reflections. Crystal data for complex VII: space group P2'2'2{\textquoteright}, a = 9.132 (7) {\AA}, b = 17.028 (7){\AA}, c = 28.084 (7) {\AA},V= 4367.42 {\AA}3, Z = 4, R = 9.8% from 2783 reflections. Both complexes have distorted pentagonal-bipyramidal geometries. Chemical or electrochemical reduction of [MoCl(S2CNR2)2(dppe)]+ under CO gives [Mo(CO)(S2CNR2)2(dppe)], whereas under N2 or Ar dimeric [{Mo(S2CNR2)2(dppe)}2]2+ is formed. The redox chemistry of these species and other intermediates has been studied by a range of electrochemical techniques, and reduction mechanisms are proposed, together with the implications for the binding of small molecules to the reductively generated site.",

author = "Dilworth, {Jonathan R.} and Neaves, {Bryan D.} and Pickett, {Christopher J.} and Joseph Chatt and Zubieta, {Jon A.}",

year = "1983",

month = nov,

doi = "10.1021/ic00166a009",

language = "English (US)",

volume = "22",

pages = "3524--3529",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "24",

}

TY - JOUR

T1 - Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S2CNEt2)2(Ph2PCH2CH2PPh2)][BF4] and [MoCl(S2CNEt2)2(PPh2Me)2][PF6] and the Mechanism of Their Electrochemical Reduction

AU - Dilworth, Jonathan R.

AU - Neaves, Bryan D.

AU - Pickett, Christopher J.

AU - Chatt, Joseph

AU - Zubieta, Jon A.

PY - 1983/11

Y1 - 1983/11

N2 - The complexes [MoX(S2CNR2)2P2] [Y] or [MoX2(S2CNR2)2P] (R2 = Me2, Et2, or (CH2)5; X = CI or Br; Y = Cl, PF6, BF4, or BPh4; P = 1/2 Ph2PCH2CH2PPh2, PPh2Me, PMe2Ph, or PEt2Ph) are prepared from [MoOX2(S2CNR2)2] and P. The crystal and molecular structures of [MoCl(S2CNEt2)2(dppe)] [BF4] (I) and [MoCl(S2CNEt2)2(PPh2Me)2] [PF6] (VII) have been determined by single-crystal X-ray diffraction methods. Crystal data for complex I: space group P1, a = 11.422 (7) Å, b = 11.902 (9) Å, c = 16.900 (8) Å, α = 104.64 (l)°,β = 101.65 (2)°, γ = 103.34 (1)°, V= 2078.60 Å3, Z = 2, R = 6.8% from 5429 reflections. Crystal data for complex VII: space group P2'2'2’, a = 9.132 (7) Å, b = 17.028 (7)Å, c = 28.084 (7) Å,V= 4367.42 Å3, Z = 4, R = 9.8% from 2783 reflections. Both complexes have distorted pentagonal-bipyramidal geometries. Chemical or electrochemical reduction of [MoCl(S2CNR2)2(dppe)]+ under CO gives [Mo(CO)(S2CNR2)2(dppe)], whereas under N2 or Ar dimeric [{Mo(S2CNR2)2(dppe)}2]2+ is formed. The redox chemistry of these species and other intermediates has been studied by a range of electrochemical techniques, and reduction mechanisms are proposed, together with the implications for the binding of small molecules to the reductively generated site.

AB - The complexes [MoX(S2CNR2)2P2] [Y] or [MoX2(S2CNR2)2P] (R2 = Me2, Et2, or (CH2)5; X = CI or Br; Y = Cl, PF6, BF4, or BPh4; P = 1/2 Ph2PCH2CH2PPh2, PPh2Me, PMe2Ph, or PEt2Ph) are prepared from [MoOX2(S2CNR2)2] and P. The crystal and molecular structures of [MoCl(S2CNEt2)2(dppe)] [BF4] (I) and [MoCl(S2CNEt2)2(PPh2Me)2] [PF6] (VII) have been determined by single-crystal X-ray diffraction methods. Crystal data for complex I: space group P1, a = 11.422 (7) Å, b = 11.902 (9) Å, c = 16.900 (8) Å, α = 104.64 (l)°,β = 101.65 (2)°, γ = 103.34 (1)°, V= 2078.60 Å3, Z = 2, R = 6.8% from 5429 reflections. Crystal data for complex VII: space group P2'2'2’, a = 9.132 (7) Å, b = 17.028 (7)Å, c = 28.084 (7) Å,V= 4367.42 Å3, Z = 4, R = 9.8% from 2783 reflections. Both complexes have distorted pentagonal-bipyramidal geometries. Chemical or electrochemical reduction of [MoCl(S2CNR2)2(dppe)]+ under CO gives [Mo(CO)(S2CNR2)2(dppe)], whereas under N2 or Ar dimeric [{Mo(S2CNR2)2(dppe)}2]2+ is formed. The redox chemistry of these species and other intermediates has been studied by a range of electrochemical techniques, and reduction mechanisms are proposed, together with the implications for the binding of small molecules to the reductively generated site.

UR - http://www.scopus.com/inward/record.url?scp=33845550081&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33845550081&partnerID=8YFLogxK

U2 - 10.1021/ic00166a009

DO - 10.1021/ic00166a009

M3 - Article

AN - SCOPUS:33845550081

SN - 0020-1669

VL - 22

SP - 3524

EP - 3529

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -