Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of...

Shuncheng Liu; Jon Zubieta

doi:10.1016/S0277-5387(00)83831-0

Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of...

Shuncheng Liu, Jon Zubieta

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

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Abstract

Title full: Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of molybdenum(VI), (n-Bu₄N)[MoO₂(C₆H₅NNC(X)NNC ₆H₅)(C₆H₅NNC(X)NN(H)C ₆H₅)] (X = O or S) and (n-Bu₄N)[MoOCl₃(C₆H₅NNC(O)NN C₆H₅)]; isolation of 2,3-diphenyltetrazolium-5-thiolate, C₆H₅NNC(S)NNC₆H₅, from the reaction of diphenylthiocarbazone with molybdate. Reaction of α-(Bu₄N)₄[Mo₈O₂₆] with diphenylcarbazone (dpcH₂) yields the red crystalline complex (Bu₄N)[MoO₂(C₆H₅NNC(O)NNC ₆H₅)(C₆H₅(H)NNC(O)NNC₆H₅)] (I), a complex displaying two distinct chelate ring types. Treatment of I with HCl yields (Bu₄N)[MoOCl₃(C₆H₅NNC(O)NNC ₆H₅)] (III), a pseudo-octahedral complex with the [MoOCl₃]⁺ core. The reaction of α-(Bu₄N)₄[Mo₈O₂₆] with diphenylcarbazone (dptcH₂) gave a complex analogous to I, (Bu₄N)[MoO₂(C₆H₅NNC(S)NNC ₆H₅)(C₆H₅(H)NNC(S) NNC₆H₅)] (II) and, surprisingly, 2,3-diphenyltetrazolium-5-thiolate, C₆H₅NNC(S)NNC₆H₅ (IV). Complex I displays a pseudo-octahedral geometry with MoO₄N₂ coordination and presents distinct geometries for the chemically inequivalent ligand types (dpc)^2- and (dpcH)^-. The structure of II is analogous to that of I with MoO₂N₂S₂ coordination geometry but, more significantly, reveals the site of protonation of the (dptcH)^- ligand as the terminal exocyclic nitrogen. Crystal data: I, monoclinic space group P2₁/n, a = 11.026(3), b = 21.600(5), c = 18.851(4) Å, β = 98.04(1)°, V = 4445.1(12) Å³, 2804 reflections, R = 0.065; II, monoclinic space group P2₁/c, a = 12.209(3), b = 20.090(4), c = 19.097(2) Å, β = 96.45(1)°, V = 4654.4(9) Å³, 3835 reflections, R = 0.047; III, P2₁/n, a = 14.853(2), b = 15.698(4), c = 17.062(4) Å, β = 90.10(1)°, V = 3978.2(10) Å³, 3128 reflections, R = 0.082; IV, C2/c, a = 14.755(2), b = 12.193(2), c = 6.958(2) Å, β = 97.42(2)°, V = 1241.3(8), 1055 reflections, R = 0.047.

Original language	English (US)
Pages (from-to)	677-688
Number of pages	12
Journal	Polyhedron
Volume	8
Issue number	5
DOIs	https://doi.org/10.1016/S0277-5387(00)83831-0
State	Published - 1989
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0277-5387(00)83831-0

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@article{0222c51acbdc4189ac186d4c42bcca0e,

title = "Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of...",

abstract = "Title full: Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of molybdenum(VI), (n-Bu4N)[MoO2(C6H5NNC(X)NNC 6H5)(C6H5NNC(X)NN(H)C 6H5)] (X = O or S) and (n-Bu4N)[MoOCl3(C6H5NNC(O)NN C6H5)]; isolation of 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5, from the reaction of diphenylthiocarbazone with molybdate. Reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dpcH2) yields the red crystalline complex (Bu4N)[MoO2(C6H5NNC(O)NNC 6H5)(C6H5(H)NNC(O)NNC 6H5)] (I), a complex displaying two distinct chelate ring types. Treatment of I with HCl yields (Bu4N)[MoOCl3(C6H5NNC(O)NNC 6H5)] (III), a pseudo-octahedral complex with the [MoOCl3]+ core. The reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dptcH2) gave a complex analogous to I, (Bu4N)[MoO2(C6H5NNC(S)NNC 6H5)(C6H5(H)NNC(S) NNC6H5)] (II) and, surprisingly, 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5 (IV). Complex I displays a pseudo-octahedral geometry with MoO4N2 coordination and presents distinct geometries for the chemically inequivalent ligand types (dpc)2- and (dpcH)-. The structure of II is analogous to that of I with MoO2N2S2 coordination geometry but, more significantly, reveals the site of protonation of the (dptcH)- ligand as the terminal exocyclic nitrogen. Crystal data: I, monoclinic space group P21/n, a = 11.026(3), b = 21.600(5), c = 18.851(4) {\AA}, β = 98.04(1)°, V = 4445.1(12) {\AA}3, 2804 reflections, R = 0.065; II, monoclinic space group P21/c, a = 12.209(3), b = 20.090(4), c = 19.097(2) {\AA}, β = 96.45(1)°, V = 4654.4(9) {\AA}3, 3835 reflections, R = 0.047; III, P21/n, a = 14.853(2), b = 15.698(4), c = 17.062(4) {\AA}, β = 90.10(1)°, V = 3978.2(10) {\AA}3, 3128 reflections, R = 0.082; IV, C2/c, a = 14.755(2), b = 12.193(2), c = 6.958(2) {\AA}, β = 97.42(2)°, V = 1241.3(8), 1055 reflections, R = 0.047.",

author = "Shuncheng Liu and Jon Zubieta",

year = "1989",

doi = "10.1016/S0277-5387(00)83831-0",

language = "English (US)",

volume = "8",

pages = "677--688",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier",

number = "5",

}

TY - JOUR

T1 - Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of...

AU - Liu, Shuncheng

AU - Zubieta, Jon

PY - 1989

Y1 - 1989

N2 - Title full: Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of molybdenum(VI), (n-Bu4N)[MoO2(C6H5NNC(X)NNC 6H5)(C6H5NNC(X)NN(H)C 6H5)] (X = O or S) and (n-Bu4N)[MoOCl3(C6H5NNC(O)NN C6H5)]; isolation of 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5, from the reaction of diphenylthiocarbazone with molybdate. Reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dpcH2) yields the red crystalline complex (Bu4N)[MoO2(C6H5NNC(O)NNC 6H5)(C6H5(H)NNC(O)NNC 6H5)] (I), a complex displaying two distinct chelate ring types. Treatment of I with HCl yields (Bu4N)[MoOCl3(C6H5NNC(O)NNC 6H5)] (III), a pseudo-octahedral complex with the [MoOCl3]+ core. The reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dptcH2) gave a complex analogous to I, (Bu4N)[MoO2(C6H5NNC(S)NNC 6H5)(C6H5(H)NNC(S) NNC6H5)] (II) and, surprisingly, 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5 (IV). Complex I displays a pseudo-octahedral geometry with MoO4N2 coordination and presents distinct geometries for the chemically inequivalent ligand types (dpc)2- and (dpcH)-. The structure of II is analogous to that of I with MoO2N2S2 coordination geometry but, more significantly, reveals the site of protonation of the (dptcH)- ligand as the terminal exocyclic nitrogen. Crystal data: I, monoclinic space group P21/n, a = 11.026(3), b = 21.600(5), c = 18.851(4) Å, β = 98.04(1)°, V = 4445.1(12) Å3, 2804 reflections, R = 0.065; II, monoclinic space group P21/c, a = 12.209(3), b = 20.090(4), c = 19.097(2) Å, β = 96.45(1)°, V = 4654.4(9) Å3, 3835 reflections, R = 0.047; III, P21/n, a = 14.853(2), b = 15.698(4), c = 17.062(4) Å, β = 90.10(1)°, V = 3978.2(10) Å3, 3128 reflections, R = 0.082; IV, C2/c, a = 14.755(2), b = 12.193(2), c = 6.958(2) Å, β = 97.42(2)°, V = 1241.3(8), 1055 reflections, R = 0.047.

AB - Title full: Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of molybdenum(VI), (n-Bu4N)[MoO2(C6H5NNC(X)NNC 6H5)(C6H5NNC(X)NN(H)C 6H5)] (X = O or S) and (n-Bu4N)[MoOCl3(C6H5NNC(O)NN C6H5)]; isolation of 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5, from the reaction of diphenylthiocarbazone with molybdate. Reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dpcH2) yields the red crystalline complex (Bu4N)[MoO2(C6H5NNC(O)NNC 6H5)(C6H5(H)NNC(O)NNC 6H5)] (I), a complex displaying two distinct chelate ring types. Treatment of I with HCl yields (Bu4N)[MoOCl3(C6H5NNC(O)NNC 6H5)] (III), a pseudo-octahedral complex with the [MoOCl3]+ core. The reaction of α-(Bu4N)4[Mo8O26] with diphenylcarbazone (dptcH2) gave a complex analogous to I, (Bu4N)[MoO2(C6H5NNC(S)NNC 6H5)(C6H5(H)NNC(S) NNC6H5)] (II) and, surprisingly, 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)NNC6H5 (IV). Complex I displays a pseudo-octahedral geometry with MoO4N2 coordination and presents distinct geometries for the chemically inequivalent ligand types (dpc)2- and (dpcH)-. The structure of II is analogous to that of I with MoO2N2S2 coordination geometry but, more significantly, reveals the site of protonation of the (dptcH)- ligand as the terminal exocyclic nitrogen. Crystal data: I, monoclinic space group P21/n, a = 11.026(3), b = 21.600(5), c = 18.851(4) Å, β = 98.04(1)°, V = 4445.1(12) Å3, 2804 reflections, R = 0.065; II, monoclinic space group P21/c, a = 12.209(3), b = 20.090(4), c = 19.097(2) Å, β = 96.45(1)°, V = 4654.4(9) Å3, 3835 reflections, R = 0.047; III, P21/n, a = 14.853(2), b = 15.698(4), c = 17.062(4) Å, β = 90.10(1)°, V = 3978.2(10) Å3, 3128 reflections, R = 0.082; IV, C2/c, a = 14.755(2), b = 12.193(2), c = 6.958(2) Å, β = 97.42(2)°, V = 1241.3(8), 1055 reflections, R = 0.047.

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UR - http://www.scopus.com/inward/citedby.url?scp=0008652139&partnerID=8YFLogxK

U2 - 10.1016/S0277-5387(00)83831-0

DO - 10.1016/S0277-5387(00)83831-0

M3 - Article

AN - SCOPUS:0008652139

SN - 0277-5387

VL - 8

SP - 677

EP - 688

JO - Polyhedron

JF - Polyhedron

IS - 5

ER -

Chemical and x-ray structural characterization of diphenylcarbazone and diphenylthiocarbazone complexes of...

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