Soluble yttrium chalcogenides: Syntheses, structures, and NMR properties of Y[η3-N(SPPh2)2]3 and Y[η2-N(SePPH2)2]2[η3-N(SePPH2)2]

Christopher G. Pernin; James A Ibers

doi:10.1021/ic990984x

Soluble yttrium chalcogenides: Syntheses, structures, and NMR properties of Y[η³-N(SPPh₂)₂]₃ and Y[η²-N(SePPH₂)₂]₂[η³-N(SePPH₂)₂]

Christopher G. Pernin, James A Ibers^*

^*Corresponding author for this work

Chemistry

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

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Abstract

The compounds Y[N(QPPh₂)₂]₃ (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reactions between Y[N(SiMe₃)₂]₃ and HN(QPPh₂)₂ in methylene chloride (CH₂Cl₂). The compounds are not isostructural. In 1, the Y atom is surrounded by three similar [N(SPPh₂)₂]^- ligands bound η³ through two S atoms and an N atom. The molecule possesses D₃ symmetry, as determined in the solid state by X-ray crystallography and in solution by ⁸⁹y and ³¹P NMR spectroscopies. In 2, the Y atom is surrounded again by three [N(SePPh₂)₂]^- ligands, but two are bound η² through the two Se atoms and the other ligand is bound η³ through the two Se atoms and an N atom. Although a fluxional process is detected in the ³¹P and ⁷⁷Se NMR spectra, a triplet is found in the ⁸⁹Y NMR spectrum of 2 (δ = 436 ppm relative to YCl₃ in D₂O, ²J(Y-P) = 5 Hz). This implies that on average the conformation, of one η³- and two η²-bound ligands is retained in solution. Crystallographic data for 1: C₇₂H₆₀N₃P₆S₆Y, rhombohedral, R3c, a = 14.927(5) Å, c = 56.047(13) Å, V = 10815(6) Å³, T = 153 K, Z = 6, and R₁(F) = 0.042 for the 1451 reflections with I > 2σ(I). Crystallographic data for 2: C₇₂H₆₀N₃P₆Se₆Y·CH₂Cl₂, monoclinic, P2₁/n, a = 13.3511(17) Å, b = 38.539(7) Å, c = 14.108(2) Å, β = 94.085(13)°, V = 7241(2) Å³, T = 153 K, Z = 4, and R₁(F) = 0.037 for the 8868 reflections with I > 2σ(I).

Original language	English (US)
Pages (from-to)	1222-1226
Number of pages	5
Journal	Inorganic chemistry
Volume	39
Issue number	6
DOIs	https://doi.org/10.1021/ic990984x
State	Published - Mar 20 2000

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic990984x

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@article{9c7a90df0b024843a90dcb565ee48268,

title = "Soluble yttrium chalcogenides: Syntheses, structures, and NMR properties of Y[η3-N(SPPh2)2]3 and Y[η2-N(SePPH2)2]2[η3-N(SePPH2)2]",

abstract = "The compounds Y[N(QPPh2)2]3 (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reactions between Y[N(SiMe3)2]3 and HN(QPPh2)2 in methylene chloride (CH2Cl2). The compounds are not isostructural. In 1, the Y atom is surrounded by three similar [N(SPPh2)2]- ligands bound η3 through two S atoms and an N atom. The molecule possesses D3 symmetry, as determined in the solid state by X-ray crystallography and in solution by 89y and 31P NMR spectroscopies. In 2, the Y atom is surrounded again by three [N(SePPh2)2]- ligands, but two are bound η2 through the two Se atoms and the other ligand is bound η3 through the two Se atoms and an N atom. Although a fluxional process is detected in the 31P and 77Se NMR spectra, a triplet is found in the 89Y NMR spectrum of 2 (δ = 436 ppm relative to YCl3 in D2O, 2J(Y-P) = 5 Hz). This implies that on average the conformation, of one η3- and two η2-bound ligands is retained in solution. Crystallographic data for 1: C72H60N3P6S6Y, rhombohedral, R3c, a = 14.927(5) {\AA}, c = 56.047(13) {\AA}, V = 10815(6) {\AA}3, T = 153 K, Z = 6, and R1(F) = 0.042 for the 1451 reflections with I > 2σ(I). Crystallographic data for 2: C72H60N3P6Se6Y·CH2Cl2, monoclinic, P21/n, a = 13.3511(17) {\AA}, b = 38.539(7) {\AA}, c = 14.108(2) {\AA}, β = 94.085(13)°, V = 7241(2) {\AA}3, T = 153 K, Z = 4, and R1(F) = 0.037 for the 8868 reflections with I > 2σ(I).",

author = "Pernin, {Christopher G.} and Ibers, {James A}",

year = "2000",

month = mar,

day = "20",

doi = "10.1021/ic990984x",

language = "English (US)",

volume = "39",

pages = "1222--1226",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "6",

}

TY - JOUR

T1 - Soluble yttrium chalcogenides

T2 - Syntheses, structures, and NMR properties of Y[η3-N(SPPh2)2]3 and Y[η2-N(SePPH2)2]2[η3-N(SePPH2)2]

AU - Pernin, Christopher G.

AU - Ibers, James A

PY - 2000/3/20

Y1 - 2000/3/20

N2 - The compounds Y[N(QPPh2)2]3 (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reactions between Y[N(SiMe3)2]3 and HN(QPPh2)2 in methylene chloride (CH2Cl2). The compounds are not isostructural. In 1, the Y atom is surrounded by three similar [N(SPPh2)2]- ligands bound η3 through two S atoms and an N atom. The molecule possesses D3 symmetry, as determined in the solid state by X-ray crystallography and in solution by 89y and 31P NMR spectroscopies. In 2, the Y atom is surrounded again by three [N(SePPh2)2]- ligands, but two are bound η2 through the two Se atoms and the other ligand is bound η3 through the two Se atoms and an N atom. Although a fluxional process is detected in the 31P and 77Se NMR spectra, a triplet is found in the 89Y NMR spectrum of 2 (δ = 436 ppm relative to YCl3 in D2O, 2J(Y-P) = 5 Hz). This implies that on average the conformation, of one η3- and two η2-bound ligands is retained in solution. Crystallographic data for 1: C72H60N3P6S6Y, rhombohedral, R3c, a = 14.927(5) Å, c = 56.047(13) Å, V = 10815(6) Å3, T = 153 K, Z = 6, and R1(F) = 0.042 for the 1451 reflections with I > 2σ(I). Crystallographic data for 2: C72H60N3P6Se6Y·CH2Cl2, monoclinic, P21/n, a = 13.3511(17) Å, b = 38.539(7) Å, c = 14.108(2) Å, β = 94.085(13)°, V = 7241(2) Å3, T = 153 K, Z = 4, and R1(F) = 0.037 for the 8868 reflections with I > 2σ(I).

AB - The compounds Y[N(QPPh2)2]3 (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reactions between Y[N(SiMe3)2]3 and HN(QPPh2)2 in methylene chloride (CH2Cl2). The compounds are not isostructural. In 1, the Y atom is surrounded by three similar [N(SPPh2)2]- ligands bound η3 through two S atoms and an N atom. The molecule possesses D3 symmetry, as determined in the solid state by X-ray crystallography and in solution by 89y and 31P NMR spectroscopies. In 2, the Y atom is surrounded again by three [N(SePPh2)2]- ligands, but two are bound η2 through the two Se atoms and the other ligand is bound η3 through the two Se atoms and an N atom. Although a fluxional process is detected in the 31P and 77Se NMR spectra, a triplet is found in the 89Y NMR spectrum of 2 (δ = 436 ppm relative to YCl3 in D2O, 2J(Y-P) = 5 Hz). This implies that on average the conformation, of one η3- and two η2-bound ligands is retained in solution. Crystallographic data for 1: C72H60N3P6S6Y, rhombohedral, R3c, a = 14.927(5) Å, c = 56.047(13) Å, V = 10815(6) Å3, T = 153 K, Z = 6, and R1(F) = 0.042 for the 1451 reflections with I > 2σ(I). Crystallographic data for 2: C72H60N3P6Se6Y·CH2Cl2, monoclinic, P21/n, a = 13.3511(17) Å, b = 38.539(7) Å, c = 14.108(2) Å, β = 94.085(13)°, V = 7241(2) Å3, T = 153 K, Z = 4, and R1(F) = 0.037 for the 8868 reflections with I > 2σ(I).

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U2 - 10.1021/ic990984x

DO - 10.1021/ic990984x

M3 - Article

C2 - 12526414

AN - SCOPUS:0034688993

SN - 0020-1669

VL - 39

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EP - 1226

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 6

ER -

Soluble yttrium chalcogenides: Syntheses, structures, and NMR properties of Y[η³-N(SPPh₂)₂]₃ and Y[η²-N(SePPH₂)₂]₂[η³-N(SePPH₂)₂]

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CCDC 143628: Experimental Crystal Structure Determination

CCDC 143630: Experimental Crystal Structure Determination

CCDC 143629: Experimental Crystal Structure Determination

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Soluble yttrium chalcogenides: Syntheses, structures, and NMR properties of Y[η3-N(SPPh2)2]3 and Y[η2-N(SePPH2)2]2[η3-N(SePPH2)2]

Abstract

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CCDC 143628: Experimental Crystal Structure Determination

CCDC 143630: Experimental Crystal Structure Determination

CCDC 143629: Experimental Crystal Structure Determination

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Soluble yttrium chalcogenides: Syntheses, structures, and NMR properties of Y[η³-N(SPPh₂)₂]₃ and Y[η²-N(SePPH₂)₂]₂[η³-N(SePPH₂)₂]