Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an

Hyunkyu Kang; Shuncheng Liu; Shahid N. Shaikh; Terrence Nicholson; Jon Zubieta

doi:10.1021/ic00304a024

Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an

Hyunkyu Kang, Shuncheng Liu, Shahid N. Shaikh, Terrence Nicholson, Jon Zubieta

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Abstract

The tetranuclear methoxooxomolybdate [MePPh₃]₂[Mo40io(OCH₃)₆] ([MePPh₃]₂[I]) provides a synthetic precursor and a structural prototype for a class of tetranuclear polyoxomolybdate coordination complexes. Reaction of I with Me₃SiCl yields [Mo₄O₁₀(OCH₃)₄Cl₂]₁₂“ (II), which in turn may be reduced by thiols to yield a mixed-valence Mo(VI)/Mo(V) infecies, [n-Bu₄N]2fM04O₈(OCH₃)4Cl₄] ([/!-Bu₄N]₂[III]). In the presence of chelating ligands, I reacts to give tetranuclear derivatives of the class [«-Bu₄N]2[Mo₄O₁₀(OCH₃)₂(LL)₂], where LL = catecholate ([/i-Bu₄N]₂[IVa]), 3-/erf-butylcatecholate ([fl-Bu₄N]₂[IVb]), naphthalene-2,3-diolate ([/i-Bu₄N]₂[IVc]), o-aminophenolate ([/i-Bu₄N]2[IVd]). Peripheral oxo groups of complexes IVa-d may be replaced by diazenido groups in condensation type reactions to give the tetranuclear complexes [/i-Bu₄N]₂[Mo₄0₆(OCH₃)2-(LL)₂(NNC₆H₅)₄] ([/i-Bu₄N]₂[Va-d]). The related binuclear class of complexes [Mo₂(OCH₃)₂(NNC₆H₅)₄(LL)₂]ⁿ (Vla-d) has also been synthesized. Crystal data; I, triclinic, inface group Pi, a = 10.185 (2) Å, b = 10.848 (2) Å, c = 11.686 (2) Å, α = 92.55 (2)°, β = 107.15 (2)°, γ = 96.79 (2)°, 1220.8 (6) Å₃₄₅, Z= 1, 2798 reflections (Mo Ka, X = 0.71073 Å in all cases), R = 0.0246; II, triclinic, inface group Pi, a = 10.186 (4) Å, b = 11.722 (3) Å, c = 13.173 (4) Å, α = 109.35 (2)°, β 107.43 (1)°, ϒ = 96.99 (1)°, V = 1372.6 (6) Å₃, Z = 1, 3020 reflections, R = 0.0407; III, monoclinic, inface group Pli/n, a = 10.653 (3) A, b = 13.184 (4) Å, c = 12.703 (4) A, β = 98.12 (1)°, V = 1766.1 (8) Å₃, Z = 2, 2424 reflections, R = 0.0469; IVa, monoclinic, inface group Plda, a = 18.494 (3) A, b = 16.192 (4) A, c_= 20.411 (3) Å, β = 107.51 (1)°, V = 5822.6 (10) Å₃, Z = 4, 3832 reflections, R = 0.0566; Vc, rhombohedral, inface group R3 (hexagonal indices), a = 26.609 (4) Å, c = 31.844 (7) Å, K= 19519.4 (9) Å₃, Z = 9, 2730 reflections, R = 0.0616; Vd, monoclinic, inface group P2₁/n a = 24.675 (2) Å, b = 19.937 (3) Å, c = 17.295 (4) Å, β= 112.62 (2)°, V= 7854.3 (11) Å, Z = 4, 4015 reflections, R-0.0781; VId, triclinic, inface group Pl,fl = 9.500 (2) Å, b = 11.942 (3) Å, c = 12.026 (2) Å, a = 61.94 (1)°, β = 81.80 (2)°, y = 86.11 (2)°, V= 1191.7 (10) Å₃, Z = 1, 2059 reflections, R = 0.0441.

Original language	English (US)
Pages (from-to)	920-933
Number of pages	14
Journal	Inorganic Chemistry
Volume	28
Issue number	5
DOIs	https://doi.org/10.1021/ic00304a024
State	Published - Mar 1 1989
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Kang, H., Liu, S., Shaikh, S. N., Nicholson, T., & Zubieta, J. (1989). Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an. Inorganic Chemistry, 28(5), 920-933. https://doi.org/10.1021/ic00304a024

Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an. / Kang, Hyunkyu; Liu, Shuncheng; Shaikh, Shahid N. et al.
In: Inorganic Chemistry, Vol. 28, No. 5, 01.03.1989, p. 920-933.

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

Kang, H, Liu, S, Shaikh, SN, Nicholson, T & Zubieta, J 1989, 'Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an', Inorganic Chemistry, vol. 28, no. 5, pp. 920-933. https://doi.org/10.1021/ic00304a024

Kang H, Liu S, Shaikh SN, Nicholson T, Zubieta J. Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an. Inorganic Chemistry. 1989 Mar 1;28(5):920-933. doi: 10.1021/ic00304a024

Kang, Hyunkyu ; Liu, Shuncheng ; Shaikh, Shahid N. et al. / Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an. In: Inorganic Chemistry. 1989 ; Vol. 28, No. 5. pp. 920-933.

@article{2cf9efb369fd4fc6915961614b2dbbd6,

title = "Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an",

abstract = "The tetranuclear methoxooxomolybdate [MePPh3]2[Mo40io(OCH3)6] ([MePPh3]2[I]) provides a synthetic precursor and a structural prototype for a class of tetranuclear polyoxomolybdate coordination complexes. Reaction of I with Me3SiCl yields [Mo4O10(OCH3)4Cl2]12“ (II), which in turn may be reduced by thiols to yield a mixed-valence Mo(VI)/Mo(V) infecies, [n-Bu4N]2fM04O8(OCH3)4Cl4] ([/!-Bu4N]2[III]). In the presence of chelating ligands, I reacts to give tetranuclear derivatives of the class [«-Bu4N]2[Mo4O10(OCH3)2(LL)2], where LL = catecholate ([/i-Bu4N]2[IVa]), 3-/erf-butylcatecholate ([fl-Bu4N]2[IVb]), naphthalene-2,3-diolate ([/i-Bu4N]2[IVc]), o-aminophenolate ([/i-Bu4N]2[IVd]). Peripheral oxo groups of complexes IVa-d may be replaced by diazenido groups in condensation type reactions to give the tetranuclear complexes [/i-Bu4N]2[Mo406(OCH3)2-(LL)2(NNC6H5)4] ([/i-Bu4N]2[Va-d]). The related binuclear class of complexes [Mo2(OCH3)2(NNC6H5)4(LL)2]n (Vla-d) has also been synthesized. Crystal data; I, triclinic, inface group Pi, a = 10.185 (2) {\AA}, b = 10.848 (2) {\AA}, c = 11.686 (2) {\AA}, α = 92.55 (2)°, β = 107.15 (2)°, γ = 96.79 (2)°, 1220.8 (6) {\AA}345, Z= 1, 2798 reflections (Mo Ka, X = 0.71073 {\AA} in all cases), R = 0.0246; II, triclinic, inface group Pi, a = 10.186 (4) {\AA}, b = 11.722 (3) {\AA}, c = 13.173 (4) {\AA}, α = 109.35 (2)°, β 107.43 (1)°, ϒ = 96.99 (1)°, V = 1372.6 (6) {\AA}3, Z = 1, 3020 reflections, R = 0.0407; III, monoclinic, inface group Pli/n, a = 10.653 (3) A, b = 13.184 (4) {\AA}, c = 12.703 (4) A, β = 98.12 (1)°, V = 1766.1 (8) {\AA}3, Z = 2, 2424 reflections, R = 0.0469; IVa, monoclinic, inface group Plda, a = 18.494 (3) A, b = 16.192 (4) A, c_= 20.411 (3) {\AA}, β = 107.51 (1)°, V = 5822.6 (10) {\AA}3, Z = 4, 3832 reflections, R = 0.0566; Vc, rhombohedral, inface group R3 (hexagonal indices), a = 26.609 (4) {\AA}, c = 31.844 (7) {\AA}, K= 19519.4 (9) {\AA}3, Z = 9, 2730 reflections, R = 0.0616; Vd, monoclinic, inface group P21/n a = 24.675 (2) {\AA}, b = 19.937 (3) {\AA}, c = 17.295 (4) {\AA}, β= 112.62 (2)°, V= 7854.3 (11) {\AA}, Z = 4, 4015 reflections, R-0.0781; VId, triclinic, inface group Pl,fl = 9.500 (2) {\AA}, b = 11.942 (3) {\AA}, c = 12.026 (2) {\AA}, a = 61.94 (1)°, β = 81.80 (2)°, y = 86.11 (2)°, V= 1191.7 (10) {\AA}3, Z = 1, 2059 reflections, R = 0.0441.",

author = "Hyunkyu Kang and Shuncheng Liu and Shaikh, {Shahid N.} and Terrence Nicholson and Jon Zubieta",

year = "1989",

month = mar,

day = "1",

doi = "10.1021/ic00304a024",

language = "English (US)",

volume = "28",

pages = "920--933",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an

AU - Kang, Hyunkyu

AU - Liu, Shuncheng

AU - Shaikh, Shahid N.

AU - Nicholson, Terrence

AU - Zubieta, Jon

PY - 1989/3/1

Y1 - 1989/3/1

N2 - The tetranuclear methoxooxomolybdate [MePPh3]2[Mo40io(OCH3)6] ([MePPh3]2[I]) provides a synthetic precursor and a structural prototype for a class of tetranuclear polyoxomolybdate coordination complexes. Reaction of I with Me3SiCl yields [Mo4O10(OCH3)4Cl2]12“ (II), which in turn may be reduced by thiols to yield a mixed-valence Mo(VI)/Mo(V) infecies, [n-Bu4N]2fM04O8(OCH3)4Cl4] ([/!-Bu4N]2[III]). In the presence of chelating ligands, I reacts to give tetranuclear derivatives of the class [«-Bu4N]2[Mo4O10(OCH3)2(LL)2], where LL = catecholate ([/i-Bu4N]2[IVa]), 3-/erf-butylcatecholate ([fl-Bu4N]2[IVb]), naphthalene-2,3-diolate ([/i-Bu4N]2[IVc]), o-aminophenolate ([/i-Bu4N]2[IVd]). Peripheral oxo groups of complexes IVa-d may be replaced by diazenido groups in condensation type reactions to give the tetranuclear complexes [/i-Bu4N]2[Mo406(OCH3)2-(LL)2(NNC6H5)4] ([/i-Bu4N]2[Va-d]). The related binuclear class of complexes [Mo2(OCH3)2(NNC6H5)4(LL)2]n (Vla-d) has also been synthesized. Crystal data; I, triclinic, inface group Pi, a = 10.185 (2) Å, b = 10.848 (2) Å, c = 11.686 (2) Å, α = 92.55 (2)°, β = 107.15 (2)°, γ = 96.79 (2)°, 1220.8 (6) Å345, Z= 1, 2798 reflections (Mo Ka, X = 0.71073 Å in all cases), R = 0.0246; II, triclinic, inface group Pi, a = 10.186 (4) Å, b = 11.722 (3) Å, c = 13.173 (4) Å, α = 109.35 (2)°, β 107.43 (1)°, ϒ = 96.99 (1)°, V = 1372.6 (6) Å3, Z = 1, 3020 reflections, R = 0.0407; III, monoclinic, inface group Pli/n, a = 10.653 (3) A, b = 13.184 (4) Å, c = 12.703 (4) A, β = 98.12 (1)°, V = 1766.1 (8) Å3, Z = 2, 2424 reflections, R = 0.0469; IVa, monoclinic, inface group Plda, a = 18.494 (3) A, b = 16.192 (4) A, c_= 20.411 (3) Å, β = 107.51 (1)°, V = 5822.6 (10) Å3, Z = 4, 3832 reflections, R = 0.0566; Vc, rhombohedral, inface group R3 (hexagonal indices), a = 26.609 (4) Å, c = 31.844 (7) Å, K= 19519.4 (9) Å3, Z = 9, 2730 reflections, R = 0.0616; Vd, monoclinic, inface group P21/n a = 24.675 (2) Å, b = 19.937 (3) Å, c = 17.295 (4) Å, β= 112.62 (2)°, V= 7854.3 (11) Å, Z = 4, 4015 reflections, R-0.0781; VId, triclinic, inface group Pl,fl = 9.500 (2) Å, b = 11.942 (3) Å, c = 12.026 (2) Å, a = 61.94 (1)°, β = 81.80 (2)°, y = 86.11 (2)°, V= 1191.7 (10) Å3, Z = 1, 2059 reflections, R = 0.0441.

AB - The tetranuclear methoxooxomolybdate [MePPh3]2[Mo40io(OCH3)6] ([MePPh3]2[I]) provides a synthetic precursor and a structural prototype for a class of tetranuclear polyoxomolybdate coordination complexes. Reaction of I with Me3SiCl yields [Mo4O10(OCH3)4Cl2]12“ (II), which in turn may be reduced by thiols to yield a mixed-valence Mo(VI)/Mo(V) infecies, [n-Bu4N]2fM04O8(OCH3)4Cl4] ([/!-Bu4N]2[III]). In the presence of chelating ligands, I reacts to give tetranuclear derivatives of the class [«-Bu4N]2[Mo4O10(OCH3)2(LL)2], where LL = catecholate ([/i-Bu4N]2[IVa]), 3-/erf-butylcatecholate ([fl-Bu4N]2[IVb]), naphthalene-2,3-diolate ([/i-Bu4N]2[IVc]), o-aminophenolate ([/i-Bu4N]2[IVd]). Peripheral oxo groups of complexes IVa-d may be replaced by diazenido groups in condensation type reactions to give the tetranuclear complexes [/i-Bu4N]2[Mo406(OCH3)2-(LL)2(NNC6H5)4] ([/i-Bu4N]2[Va-d]). The related binuclear class of complexes [Mo2(OCH3)2(NNC6H5)4(LL)2]n (Vla-d) has also been synthesized. Crystal data; I, triclinic, inface group Pi, a = 10.185 (2) Å, b = 10.848 (2) Å, c = 11.686 (2) Å, α = 92.55 (2)°, β = 107.15 (2)°, γ = 96.79 (2)°, 1220.8 (6) Å345, Z= 1, 2798 reflections (Mo Ka, X = 0.71073 Å in all cases), R = 0.0246; II, triclinic, inface group Pi, a = 10.186 (4) Å, b = 11.722 (3) Å, c = 13.173 (4) Å, α = 109.35 (2)°, β 107.43 (1)°, ϒ = 96.99 (1)°, V = 1372.6 (6) Å3, Z = 1, 3020 reflections, R = 0.0407; III, monoclinic, inface group Pli/n, a = 10.653 (3) A, b = 13.184 (4) Å, c = 12.703 (4) A, β = 98.12 (1)°, V = 1766.1 (8) Å3, Z = 2, 2424 reflections, R = 0.0469; IVa, monoclinic, inface group Plda, a = 18.494 (3) A, b = 16.192 (4) A, c_= 20.411 (3) Å, β = 107.51 (1)°, V = 5822.6 (10) Å3, Z = 4, 3832 reflections, R = 0.0566; Vc, rhombohedral, inface group R3 (hexagonal indices), a = 26.609 (4) Å, c = 31.844 (7) Å, K= 19519.4 (9) Å3, Z = 9, 2730 reflections, R = 0.0616; Vd, monoclinic, inface group P21/n a = 24.675 (2) Å, b = 19.937 (3) Å, c = 17.295 (4) Å, β= 112.62 (2)°, V= 7854.3 (11) Å, Z = 4, 4015 reflections, R-0.0781; VId, triclinic, inface group Pl,fl = 9.500 (2) Å, b = 11.942 (3) Å, c = 12.026 (2) Å, a = 61.94 (1)°, β = 81.80 (2)°, y = 86.11 (2)°, V= 1191.7 (10) Å3, Z = 1, 2059 reflections, R = 0.0441.

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Synthesis and structural investigation of polyoxomolybdate coordination compounds displaying a tetranuclear core. Crystal and molecular structures of [Bu4N]2[Mo4O10(OMe)2(OC6H4O)2] and to the diazenido complexes [Bu4N]2[Mo4O6(OMe)2(HNC6H4O)2(NNC6H5)4] an

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