Preparations, Structures, and Reactions of Molybdenum Complexes of Triorgano Silylated Pyridine-2-thiols

Eric Block; Michael Gernon; Gabriel Ofori-Okai; Hyunkyu Kang; Jon Zubieta

doi:10.1021/ic00008a012

Preparations, Structures, and Reactions of Molybdenum Complexes of Triorgano Silylated Pyridine-2-thiols

Eric Block, Michael Gernon, Gabriel Ofori-Okai, Hyunkyu Kang, Jon Zubieta

Department of Chemistry

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

64 Scopus citations

Abstract

Reactions of molybdenum halide precursors with 3-(trimethylsilyl)pyridine-2-thiol (1) or 3, 6-bis(tert-butyldimethylsilyl)- pyridine-2-thiol (2) yield a variety of mononuclear and binuclear Mo(III) and Mo(IV) complexes depending on reaction conditions. Illustrative of these classes of complexes are the species [MoCl₄(2-SC₅H₃NH-3-SiMe3)₂] (3), [MoCl₃{2-SC₅H₂NH-3,6- (SiMe₂Bu^t)₂}₃] (4), [MoCl₄{2-SC₅H₂NH-3,6-(SiMe₂Bu^t)₂}₂]•(C₂H₅)₂O (6), (Ph₄P)[MoBr₄(2-SC₅H₃NH-3-SiMe₃)₂] (7), and [MoBr₃(2-SC₅H₃NH-3-SiMe₃)₃] (8). Reactions of 3 with molecular oxygen in excess and in stoichiometric quantities yield [Mo₂O₃(2-SC₅H₃N-3-SiMe₃)₄ (9) and [MoOCl(2-SC₅H₃N-3-SiMe₃)₂] (10), respectively. In contrast, 7 reacts with O₂ to yield (Ph₄P)[MoOBr3(2-SC₅H₃N-3-SiMe3)] (11). Organohydrazine ligands react with 3 by halide displacement and formal oxidation to yield the Mo(VI) species [MoCl₂(2-SC₅H₃N-3-SiMe3)₂(NNMePh)] (12) and [Mo(NNMePh)₂(2-SC₅H₃N-3-SiMe3)₂] (13). Complex 12 exhibits a seven-coordinate pentagonal-bipyramidal geometry similar to that of [Mo(NNMePh)(SC₆H₄PPhC₆H₄S)₂] (17). Reductions of 3 and 6 with hydrazine yield the binuclear Mo(III) complexes [Mo₂Cl₆(2-SC₅H₃NH-3-SiMe₃)₃]•2CH₃CN (14) and [Mo₂Cl₆{(2-SC₅H₂NH-3,6-(SiMe₂Bu^t)₂}₃] (15), respectively. Crystal data: 4, monoclinic P2₁/n, a = 17.644 (5) Å, b = 17.067 (5) Å, c = 25.798 (5) Å, β = 99.17 (1)°, V= 7669.8 (11) Å³, Z = 4, 2472 reflections, R = 0.089; 6, orthorhombic Pcan, a = 16.245 (5) Å, b = 13.531 (4) Å, c = 23.739 (7) Å, V = 5218.4 (12) Å³, Z = 4, 1533 reflections, R = 0.073; 7, triclinio P1, a = 10.689 (1) Å, b = 14.511 (3) Å, c = 16.713 (3) Å, α = 104.15 (1)°, β = 103.58 (1)°, γ = 95.46 (1)°, V= 2411.6 (8) Å³, Z = 2, 3510 reflections, R = 0.053; 8, orthorhombic, Pbca, a = 33.376 (6) Å, b = 18.751 (4) Å,c = 11.980 (4) Å, V= 7494.6 (13) Å³, Z = 8, 2864 reflections, R = 0.032; 9, monoclinic P2₁/c, a = 11.719 (4) Å, b = 14.258 (7) Å, c = 14.081 (3) Å, β = 99.91 (2)°, V= 2317.8 (II) Å³, Z = 2, 1571 reflections, R = 0.086; 10, monoclinic P2₁/c, a = 12.858 (3) Å,b= 13.655 (3) Å, c = 13.290 (3) Å, β = 96.67 (2)°, V= 2317.7 (12) Å³, Z = 4, 1843 reflections, R = 0.083; 11, monoclinic C2/c, a = 19.806 (4) Å, b = 12.271 (3) Å,c = 32.749 (5) Å, β = 96.57 (1)°, V= 7907.4 (12) Å³, Z = 8, 2440 reflections, R = 0.083; 12, monoclinic P2₁/c, a = 10.727 (3) Å, b = 16.428 (5) Å, c = 22.800 (6) Å, β = 97.67 (2)°, V= 3981.9 (21) Å³, Z = 4, 2299 reflections, R = 0.072; 13, monoclinic C2/c, a - 22.833 (5) Å, b = 10.731 (2) Å, c = 14.645 (4) Å, β = 102.25 (1)°, V = 3506.9 (21) Å³, Z = 4, 2402 reflections, R = 0.051; 14, triclinic P1, a = 10.605 (3) Å,b= 13.277 (4) Å, c = 16.969 (5) Å, α = 79.82 (1)°, β = 84.19 (2)°, γ = 71.51 (1)°, V = 2228.0 (11) Å³, Z = 2, 2249 reflections, R = 0.053; 15, orthorhombic Pbca, a = 15.338 (4) Å, b = 30.447 (8) Å, c = 33.913 (8) Å, V = 15838.2 (27) Å³, Z = 8, 5163 reflections, R = 0.059; 17, monoclinic P2₁/n, a = 13.466 (2) Å, b = 15.023 (2) Å, c = 21.565 (3) Å, β = 100.05 (1)°, F= 4296.9 (12) Å³, Z = 4, 4337 reflections, R = 0.038.

Original language	English (US)
Pages (from-to)	1736-1747
Number of pages	12
Journal	Inorganic Chemistry
Volume	30
Issue number	8
DOIs	https://doi.org/10.1021/ic00008a012
State	Published - Apr 1 1991

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00008a012

Cite this

@article{dd0528a3c6bd4dc0a5e23957f99ac3fa,

title = "Preparations, Structures, and Reactions of Molybdenum Complexes of Triorgano Silylated Pyridine-2-thiols",

abstract = "Reactions of molybdenum halide precursors with 3-(trimethylsilyl)pyridine-2-thiol (1) or 3, 6-bis(tert-butyldimethylsilyl)- pyridine-2-thiol (2) yield a variety of mononuclear and binuclear Mo(III) and Mo(IV) complexes depending on reaction conditions. Illustrative of these classes of complexes are the species [MoCl4(2-SC5H3NH-3-SiMe3)2] (3), [MoCl3{2-SC5H2NH-3,6- (SiMe2But)2}3] (4), [MoCl4{2-SC5H2NH-3,6-(SiMe2But)2}2]•(C2H5)2O (6), (Ph4P)[MoBr4(2-SC5H3NH-3-SiMe3)2] (7), and [MoBr3(2-SC5H3NH-3-SiMe3)3] (8). Reactions of 3 with molecular oxygen in excess and in stoichiometric quantities yield [Mo2O3(2-SC5H3N-3-SiMe3)4 (9) and [MoOCl(2-SC5H3N-3-SiMe3)2] (10), respectively. In contrast, 7 reacts with O2 to yield (Ph4P)[MoOBr3(2-SC5H3N-3-SiMe3)] (11). Organohydrazine ligands react with 3 by halide displacement and formal oxidation to yield the Mo(VI) species [MoCl2(2-SC5H3N-3-SiMe3)2(NNMePh)] (12) and [Mo(NNMePh)2(2-SC5H3N-3-SiMe3)2] (13). Complex 12 exhibits a seven-coordinate pentagonal-bipyramidal geometry similar to that of [Mo(NNMePh)(SC6H4PPhC6H4S)2] (17). Reductions of 3 and 6 with hydrazine yield the binuclear Mo(III) complexes [Mo2Cl6(2-SC5H3NH-3-SiMe3)3]•2CH3CN (14) and [Mo2Cl6{(2-SC5H2NH-3,6-(SiMe2But)2}3] (15), respectively. Crystal data: 4, monoclinic P21/n, a = 17.644 (5) {\AA}, b = 17.067 (5) {\AA}, c = 25.798 (5) {\AA}, β = 99.17 (1)°, V= 7669.8 (11) {\AA}3, Z = 4, 2472 reflections, R = 0.089; 6, orthorhombic Pcan, a = 16.245 (5) {\AA}, b = 13.531 (4) {\AA}, c = 23.739 (7) {\AA}, V = 5218.4 (12) {\AA}3, Z = 4, 1533 reflections, R = 0.073; 7, triclinio P1, a = 10.689 (1) {\AA}, b = 14.511 (3) {\AA}, c = 16.713 (3) {\AA}, α = 104.15 (1)°, β = 103.58 (1)°, γ = 95.46 (1)°, V= 2411.6 (8) {\AA}3, Z = 2, 3510 reflections, R = 0.053; 8, orthorhombic, Pbca, a = 33.376 (6) {\AA}, b = 18.751 (4) {\AA},c = 11.980 (4) {\AA}, V= 7494.6 (13) {\AA}3, Z = 8, 2864 reflections, R = 0.032; 9, monoclinic P21/c, a = 11.719 (4) {\AA}, b = 14.258 (7) {\AA}, c = 14.081 (3) {\AA}, β = 99.91 (2)°, V= 2317.8 (II) {\AA}3, Z = 2, 1571 reflections, R = 0.086; 10, monoclinic P21/c, a = 12.858 (3) {\AA},b= 13.655 (3) {\AA}, c = 13.290 (3) {\AA}, β = 96.67 (2)°, V= 2317.7 (12) {\AA}3, Z = 4, 1843 reflections, R = 0.083; 11, monoclinic C2/c, a = 19.806 (4) {\AA}, b = 12.271 (3) {\AA},c = 32.749 (5) {\AA}, β = 96.57 (1)°, V= 7907.4 (12) {\AA}3, Z = 8, 2440 reflections, R = 0.083; 12, monoclinic P21/c, a = 10.727 (3) {\AA}, b = 16.428 (5) {\AA}, c = 22.800 (6) {\AA}, β = 97.67 (2)°, V= 3981.9 (21) {\AA}3, Z = 4, 2299 reflections, R = 0.072; 13, monoclinic C2/c, a - 22.833 (5) {\AA}, b = 10.731 (2) {\AA}, c = 14.645 (4) {\AA}, β = 102.25 (1)°, V = 3506.9 (21) {\AA}3, Z = 4, 2402 reflections, R = 0.051; 14, triclinic P1, a = 10.605 (3) {\AA},b= 13.277 (4) {\AA}, c = 16.969 (5) {\AA}, α = 79.82 (1)°, β = 84.19 (2)°, γ = 71.51 (1)°, V = 2228.0 (11) {\AA}3, Z = 2, 2249 reflections, R = 0.053; 15, orthorhombic Pbca, a = 15.338 (4) {\AA}, b = 30.447 (8) {\AA}, c = 33.913 (8) {\AA}, V = 15838.2 (27) {\AA}3, Z = 8, 5163 reflections, R = 0.059; 17, monoclinic P21/n, a = 13.466 (2) {\AA}, b = 15.023 (2) {\AA}, c = 21.565 (3) {\AA}, β = 100.05 (1)°, F= 4296.9 (12) {\AA}3, Z = 4, 4337 reflections, R = 0.038.",

author = "Eric Block and Michael Gernon and Gabriel Ofori-Okai and Hyunkyu Kang and Jon Zubieta",

year = "1991",

month = apr,

day = "1",

doi = "10.1021/ic00008a012",

language = "English (US)",

volume = "30",

pages = "1736--1747",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Preparations, Structures, and Reactions of Molybdenum Complexes of Triorgano Silylated Pyridine-2-thiols

AU - Block, Eric

AU - Gernon, Michael

AU - Ofori-Okai, Gabriel

AU - Kang, Hyunkyu

AU - Zubieta, Jon

PY - 1991/4/1

Y1 - 1991/4/1

N2 - Reactions of molybdenum halide precursors with 3-(trimethylsilyl)pyridine-2-thiol (1) or 3, 6-bis(tert-butyldimethylsilyl)- pyridine-2-thiol (2) yield a variety of mononuclear and binuclear Mo(III) and Mo(IV) complexes depending on reaction conditions. Illustrative of these classes of complexes are the species [MoCl4(2-SC5H3NH-3-SiMe3)2] (3), [MoCl3{2-SC5H2NH-3,6- (SiMe2But)2}3] (4), [MoCl4{2-SC5H2NH-3,6-(SiMe2But)2}2]•(C2H5)2O (6), (Ph4P)[MoBr4(2-SC5H3NH-3-SiMe3)2] (7), and [MoBr3(2-SC5H3NH-3-SiMe3)3] (8). Reactions of 3 with molecular oxygen in excess and in stoichiometric quantities yield [Mo2O3(2-SC5H3N-3-SiMe3)4 (9) and [MoOCl(2-SC5H3N-3-SiMe3)2] (10), respectively. In contrast, 7 reacts with O2 to yield (Ph4P)[MoOBr3(2-SC5H3N-3-SiMe3)] (11). Organohydrazine ligands react with 3 by halide displacement and formal oxidation to yield the Mo(VI) species [MoCl2(2-SC5H3N-3-SiMe3)2(NNMePh)] (12) and [Mo(NNMePh)2(2-SC5H3N-3-SiMe3)2] (13). Complex 12 exhibits a seven-coordinate pentagonal-bipyramidal geometry similar to that of [Mo(NNMePh)(SC6H4PPhC6H4S)2] (17). Reductions of 3 and 6 with hydrazine yield the binuclear Mo(III) complexes [Mo2Cl6(2-SC5H3NH-3-SiMe3)3]•2CH3CN (14) and [Mo2Cl6{(2-SC5H2NH-3,6-(SiMe2But)2}3] (15), respectively. Crystal data: 4, monoclinic P21/n, a = 17.644 (5) Å, b = 17.067 (5) Å, c = 25.798 (5) Å, β = 99.17 (1)°, V= 7669.8 (11) Å3, Z = 4, 2472 reflections, R = 0.089; 6, orthorhombic Pcan, a = 16.245 (5) Å, b = 13.531 (4) Å, c = 23.739 (7) Å, V = 5218.4 (12) Å3, Z = 4, 1533 reflections, R = 0.073; 7, triclinio P1, a = 10.689 (1) Å, b = 14.511 (3) Å, c = 16.713 (3) Å, α = 104.15 (1)°, β = 103.58 (1)°, γ = 95.46 (1)°, V= 2411.6 (8) Å3, Z = 2, 3510 reflections, R = 0.053; 8, orthorhombic, Pbca, a = 33.376 (6) Å, b = 18.751 (4) Å,c = 11.980 (4) Å, V= 7494.6 (13) Å3, Z = 8, 2864 reflections, R = 0.032; 9, monoclinic P21/c, a = 11.719 (4) Å, b = 14.258 (7) Å, c = 14.081 (3) Å, β = 99.91 (2)°, V= 2317.8 (II) Å3, Z = 2, 1571 reflections, R = 0.086; 10, monoclinic P21/c, a = 12.858 (3) Å,b= 13.655 (3) Å, c = 13.290 (3) Å, β = 96.67 (2)°, V= 2317.7 (12) Å3, Z = 4, 1843 reflections, R = 0.083; 11, monoclinic C2/c, a = 19.806 (4) Å, b = 12.271 (3) Å,c = 32.749 (5) Å, β = 96.57 (1)°, V= 7907.4 (12) Å3, Z = 8, 2440 reflections, R = 0.083; 12, monoclinic P21/c, a = 10.727 (3) Å, b = 16.428 (5) Å, c = 22.800 (6) Å, β = 97.67 (2)°, V= 3981.9 (21) Å3, Z = 4, 2299 reflections, R = 0.072; 13, monoclinic C2/c, a - 22.833 (5) Å, b = 10.731 (2) Å, c = 14.645 (4) Å, β = 102.25 (1)°, V = 3506.9 (21) Å3, Z = 4, 2402 reflections, R = 0.051; 14, triclinic P1, a = 10.605 (3) Å,b= 13.277 (4) Å, c = 16.969 (5) Å, α = 79.82 (1)°, β = 84.19 (2)°, γ = 71.51 (1)°, V = 2228.0 (11) Å3, Z = 2, 2249 reflections, R = 0.053; 15, orthorhombic Pbca, a = 15.338 (4) Å, b = 30.447 (8) Å, c = 33.913 (8) Å, V = 15838.2 (27) Å3, Z = 8, 5163 reflections, R = 0.059; 17, monoclinic P21/n, a = 13.466 (2) Å, b = 15.023 (2) Å, c = 21.565 (3) Å, β = 100.05 (1)°, F= 4296.9 (12) Å3, Z = 4, 4337 reflections, R = 0.038.

AB - Reactions of molybdenum halide precursors with 3-(trimethylsilyl)pyridine-2-thiol (1) or 3, 6-bis(tert-butyldimethylsilyl)- pyridine-2-thiol (2) yield a variety of mononuclear and binuclear Mo(III) and Mo(IV) complexes depending on reaction conditions. Illustrative of these classes of complexes are the species [MoCl4(2-SC5H3NH-3-SiMe3)2] (3), [MoCl3{2-SC5H2NH-3,6- (SiMe2But)2}3] (4), [MoCl4{2-SC5H2NH-3,6-(SiMe2But)2}2]•(C2H5)2O (6), (Ph4P)[MoBr4(2-SC5H3NH-3-SiMe3)2] (7), and [MoBr3(2-SC5H3NH-3-SiMe3)3] (8). Reactions of 3 with molecular oxygen in excess and in stoichiometric quantities yield [Mo2O3(2-SC5H3N-3-SiMe3)4 (9) and [MoOCl(2-SC5H3N-3-SiMe3)2] (10), respectively. In contrast, 7 reacts with O2 to yield (Ph4P)[MoOBr3(2-SC5H3N-3-SiMe3)] (11). Organohydrazine ligands react with 3 by halide displacement and formal oxidation to yield the Mo(VI) species [MoCl2(2-SC5H3N-3-SiMe3)2(NNMePh)] (12) and [Mo(NNMePh)2(2-SC5H3N-3-SiMe3)2] (13). Complex 12 exhibits a seven-coordinate pentagonal-bipyramidal geometry similar to that of [Mo(NNMePh)(SC6H4PPhC6H4S)2] (17). Reductions of 3 and 6 with hydrazine yield the binuclear Mo(III) complexes [Mo2Cl6(2-SC5H3NH-3-SiMe3)3]•2CH3CN (14) and [Mo2Cl6{(2-SC5H2NH-3,6-(SiMe2But)2}3] (15), respectively. Crystal data: 4, monoclinic P21/n, a = 17.644 (5) Å, b = 17.067 (5) Å, c = 25.798 (5) Å, β = 99.17 (1)°, V= 7669.8 (11) Å3, Z = 4, 2472 reflections, R = 0.089; 6, orthorhombic Pcan, a = 16.245 (5) Å, b = 13.531 (4) Å, c = 23.739 (7) Å, V = 5218.4 (12) Å3, Z = 4, 1533 reflections, R = 0.073; 7, triclinio P1, a = 10.689 (1) Å, b = 14.511 (3) Å, c = 16.713 (3) Å, α = 104.15 (1)°, β = 103.58 (1)°, γ = 95.46 (1)°, V= 2411.6 (8) Å3, Z = 2, 3510 reflections, R = 0.053; 8, orthorhombic, Pbca, a = 33.376 (6) Å, b = 18.751 (4) Å,c = 11.980 (4) Å, V= 7494.6 (13) Å3, Z = 8, 2864 reflections, R = 0.032; 9, monoclinic P21/c, a = 11.719 (4) Å, b = 14.258 (7) Å, c = 14.081 (3) Å, β = 99.91 (2)°, V= 2317.8 (II) Å3, Z = 2, 1571 reflections, R = 0.086; 10, monoclinic P21/c, a = 12.858 (3) Å,b= 13.655 (3) Å, c = 13.290 (3) Å, β = 96.67 (2)°, V= 2317.7 (12) Å3, Z = 4, 1843 reflections, R = 0.083; 11, monoclinic C2/c, a = 19.806 (4) Å, b = 12.271 (3) Å,c = 32.749 (5) Å, β = 96.57 (1)°, V= 7907.4 (12) Å3, Z = 8, 2440 reflections, R = 0.083; 12, monoclinic P21/c, a = 10.727 (3) Å, b = 16.428 (5) Å, c = 22.800 (6) Å, β = 97.67 (2)°, V= 3981.9 (21) Å3, Z = 4, 2299 reflections, R = 0.072; 13, monoclinic C2/c, a - 22.833 (5) Å, b = 10.731 (2) Å, c = 14.645 (4) Å, β = 102.25 (1)°, V = 3506.9 (21) Å3, Z = 4, 2402 reflections, R = 0.051; 14, triclinic P1, a = 10.605 (3) Å,b= 13.277 (4) Å, c = 16.969 (5) Å, α = 79.82 (1)°, β = 84.19 (2)°, γ = 71.51 (1)°, V = 2228.0 (11) Å3, Z = 2, 2249 reflections, R = 0.053; 15, orthorhombic Pbca, a = 15.338 (4) Å, b = 30.447 (8) Å, c = 33.913 (8) Å, V = 15838.2 (27) Å3, Z = 8, 5163 reflections, R = 0.059; 17, monoclinic P21/n, a = 13.466 (2) Å, b = 15.023 (2) Å, c = 21.565 (3) Å, β = 100.05 (1)°, F= 4296.9 (12) Å3, Z = 4, 4337 reflections, R = 0.038.

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UR - http://www.scopus.com/inward/citedby.url?scp=33751500630&partnerID=8YFLogxK

U2 - 10.1021/ic00008a012

DO - 10.1021/ic00008a012

M3 - Article

AN - SCOPUS:33751500630

SN - 0020-1669

VL - 30

SP - 1736

EP - 1747

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

Preparations, Structures, and Reactions of Molybdenum Complexes of Triorgano Silylated Pyridine-2-thiols

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