Synthesis, Structure, Spectroscopy, and Reactivity of M(Se4)2 2−Anions, M = Ni, Pd, Zn, Cd, Hg, and Mn

Mohammad A. Ansari; Charles H. Mahler; Gayatri S. Chorghade; Ying Jie Lu; James A Ibers

doi:10.1021/ic00344a036

Synthesis, Structure, Spectroscopy, and Reactivity of M(Se₄)₂ ²⁻Anions, M = Ni, Pd, Zn, Cd, Hg, and Mn

Mohammad A. Ansari, Charles H. Mahler, Gayatri S. Chorghade, Ying Jie Lu, James A Ibers

Chemistry

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Abstract

The M(Se₄)₂ ²⁻ions, M = Ni, Pd, Zn, Cd, and Hg, have been synthesized by reaction of the metal xanthate with a polyselenide solution in CH₃CN-DMF. The corresponding Mn(Se₄)₂ ²⁻ion was synthesized by reaction of MnCl₂with a polyselenide solution in DMF. The Pt(Se₄)₂ ²⁻ion was synthesized in situ by reaction of Pt(Se₄)₃ ²⁻with excess BH₄ ⁻. The crystal structures of [PEtPh₃]₂[Ni(Se₄)₂] and of [PPh₄]₂[Zn(Se₄)₂] have been determined. The Ni center in the centrosymmetric Ni(Se₄)₂ ²⁻ion is essentially square planar with Ni—Se distances of 2.298 (1) and 2.315 (1) Å. The two independent Zn(Se₄)₂ ²⁻ions have approximately tetrahedral Zn centers, but they show significant metrical differences. Zn-Se distances range from 2.450 (5) to 2.493 (6) Å. The MSe₄rings have the distorted envelope conformation. The ions (except Mn(Se₄)₂ ²⁻) show two⁷⁷Se NMR resonances. These occur for the following M (´(metal-bound Se), ppm; δ(ring Se), ppm): Ni (820; 748); Pd (893; 758); Pt (727; 642); Zn ( 127; 598); Cd (62; 608); Hg (76; 594). Trends in these resonance positions are rationalized in terms of the d-electron configurations of the metal. Reaction of the corresponding M(Se₄)₂ ²⁻ion with dimethyl acetylenedicarboxylate affords the ions M(Se₂C₂− (COOCH₃)₂)₂ ²⁻(M = Zn, Ni).

Original language	English (US)
Pages (from-to)	3832-3839
Number of pages	8
Journal	Inorganic Chemistry
Volume	29
Issue number	19
DOIs	https://doi.org/10.1021/ic00344a036
State	Published - Jan 1 1990

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Ansari, M. A., Mahler, C. H., Chorghade, G. S., Lu, Y. J., & Ibers, J. A. (1990). Synthesis, Structure, Spectroscopy, and Reactivity of M(Se₄)₂ ²⁻Anions, M = Ni, Pd, Zn, Cd, Hg, and Mn. Inorganic Chemistry, 29(19), 3832-3839. https://doi.org/10.1021/ic00344a036

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title = "Synthesis, Structure, Spectroscopy, and Reactivity of M(Se4)2 2−Anions, M = Ni, Pd, Zn, Cd, Hg, and Mn",

abstract = "The M(Se4)2 2−ions, M = Ni, Pd, Zn, Cd, and Hg, have been synthesized by reaction of the metal xanthate with a polyselenide solution in CH3CN-DMF. The corresponding Mn(Se4)2 2−ion was synthesized by reaction of MnCl2with a polyselenide solution in DMF. The Pt(Se4)2 2−ion was synthesized in situ by reaction of Pt(Se4)3 2−with excess BH4 −. The crystal structures of [PEtPh3]2[Ni(Se4)2] and of [PPh4]2[Zn(Se4)2] have been determined. The Ni center in the centrosymmetric Ni(Se4)2 2−ion is essentially square planar with Ni—Se distances of 2.298 (1) and 2.315 (1) {\AA}. The two independent Zn(Se4)2 2−ions have approximately tetrahedral Zn centers, but they show significant metrical differences. Zn-Se distances range from 2.450 (5) to 2.493 (6) {\AA}. The MSe4rings have the distorted envelope conformation. The ions (except Mn(Se4)2 2−) show two77Se NMR resonances. These occur for the following M (´(metal-bound Se), ppm; δ(ring Se), ppm): Ni (820; 748); Pd (893; 758); Pt (727; 642); Zn ( 127; 598); Cd (62; 608); Hg (76; 594). Trends in these resonance positions are rationalized in terms of the d-electron configurations of the metal. Reaction of the corresponding M(Se4)2 2−ion with dimethyl acetylenedicarboxylate affords the ions M(Se2C2− (COOCH3)2)2 2−(M = Zn, Ni).",

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T1 - Synthesis, Structure, Spectroscopy, and Reactivity of M(Se4)2 2−Anions, M = Ni, Pd, Zn, Cd, Hg, and Mn

AU - Ansari, Mohammad A.

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AU - Ibers, James A

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Y1 - 1990/1/1

N2 - The M(Se4)2 2−ions, M = Ni, Pd, Zn, Cd, and Hg, have been synthesized by reaction of the metal xanthate with a polyselenide solution in CH3CN-DMF. The corresponding Mn(Se4)2 2−ion was synthesized by reaction of MnCl2with a polyselenide solution in DMF. The Pt(Se4)2 2−ion was synthesized in situ by reaction of Pt(Se4)3 2−with excess BH4 −. The crystal structures of [PEtPh3]2[Ni(Se4)2] and of [PPh4]2[Zn(Se4)2] have been determined. The Ni center in the centrosymmetric Ni(Se4)2 2−ion is essentially square planar with Ni—Se distances of 2.298 (1) and 2.315 (1) Å. The two independent Zn(Se4)2 2−ions have approximately tetrahedral Zn centers, but they show significant metrical differences. Zn-Se distances range from 2.450 (5) to 2.493 (6) Å. The MSe4rings have the distorted envelope conformation. The ions (except Mn(Se4)2 2−) show two77Se NMR resonances. These occur for the following M (´(metal-bound Se), ppm; δ(ring Se), ppm): Ni (820; 748); Pd (893; 758); Pt (727; 642); Zn ( 127; 598); Cd (62; 608); Hg (76; 594). Trends in these resonance positions are rationalized in terms of the d-electron configurations of the metal. Reaction of the corresponding M(Se4)2 2−ion with dimethyl acetylenedicarboxylate affords the ions M(Se2C2− (COOCH3)2)2 2−(M = Zn, Ni).

AB - The M(Se4)2 2−ions, M = Ni, Pd, Zn, Cd, and Hg, have been synthesized by reaction of the metal xanthate with a polyselenide solution in CH3CN-DMF. The corresponding Mn(Se4)2 2−ion was synthesized by reaction of MnCl2with a polyselenide solution in DMF. The Pt(Se4)2 2−ion was synthesized in situ by reaction of Pt(Se4)3 2−with excess BH4 −. The crystal structures of [PEtPh3]2[Ni(Se4)2] and of [PPh4]2[Zn(Se4)2] have been determined. The Ni center in the centrosymmetric Ni(Se4)2 2−ion is essentially square planar with Ni—Se distances of 2.298 (1) and 2.315 (1) Å. The two independent Zn(Se4)2 2−ions have approximately tetrahedral Zn centers, but they show significant metrical differences. Zn-Se distances range from 2.450 (5) to 2.493 (6) Å. The MSe4rings have the distorted envelope conformation. The ions (except Mn(Se4)2 2−) show two77Se NMR resonances. These occur for the following M (´(metal-bound Se), ppm; δ(ring Se), ppm): Ni (820; 748); Pd (893; 758); Pt (727; 642); Zn ( 127; 598); Cd (62; 608); Hg (76; 594). Trends in these resonance positions are rationalized in terms of the d-electron configurations of the metal. Reaction of the corresponding M(Se4)2 2−ion with dimethyl acetylenedicarboxylate affords the ions M(Se2C2− (COOCH3)2)2 2−(M = Zn, Ni).

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