Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C6H5)4P][Pt(Se2C2(CF3)2)2]

William B. Heuer; Anne E. True; Paul N. Swepston; Brian M. Hoffman

doi:10.1021/ic00281a033

Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se₂C₂(CF₃)₂)₂]^z (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C₆H₅)₄P][Pt(Se₂C₂(CF₃)₂)₂]

William B. Heuer, Anne E. True, Paul N. Swepston, Brian M. Hoffman^*

^*Corresponding author for this work

Chemistry

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Abstract

New metal diselenolene complexes with the formula [M(Se₂C₂(CF₃)₂)₂]^z (M = Pt, z = 0, -1, -2; M = Au, z = -1) have been prepared by the reaction of bis(trifluoromethyl)diselenete, (CF₃)₂C₂Se₂, with (Ph₃P)₂PtCl₂ and (Ph₃P)AuCl, respectively; the previously known Ni and Cu analogues have been similarly obtained. Comparison of electrochemical data for these complexes with those of the corresponding metal bis(dithiolene) complexes indicates that substitution of selenium for sulfur does not dramatically alter the electronic structure. Analysis of ESR spectra of the paramagnetic [M(Se₂C₂(CF₃)₂)₂]^- (M = Ni, Pt) anions indicates that the majority (ca. 70%) of the unpaired spin is located on the four selenium atoms. The neutral complex [Pt-(Se₂C₂(CF₃)₂)₂] exhibits an unusual associational equilibrium in solution that has been studied by UV-vis and ¹⁹F NMR spectroscopy. The X-ray crystal structure of [(C₆H₅)₄P] [Pt(Se₂C₂(CF₃)₂)₂] also is reported; the coordination geometry of Pt is nominally square planar, with interatomic distances reflecting substantial multiple-bond character in the Pt-Se bonds. Crystal data: monoclinic, space group P2₁/c, with a = 18.015 (3) Å, b = 14.280 (4) Å, c = 14.627 (4) Å, β = 112.30 (2)°, V = 3481.4 (9) Å ³, and Z = 4.

Original language	English (US)
Pages (from-to)	1474-1482
Number of pages	9
Journal	Inorganic chemistry
Volume	27
Issue number	8
DOIs	https://doi.org/10.1021/ic00281a033
State	Published - Apr 1 1988

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Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00281a033

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@article{fe83ee71de3f4430af8aee019e63c67f,

title = "Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C6H5)4P][Pt(Se2C2(CF3)2)2]",

abstract = "New metal diselenolene complexes with the formula [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) have been prepared by the reaction of bis(trifluoromethyl)diselenete, (CF3)2C2Se2, with (Ph3P)2PtCl2 and (Ph3P)AuCl, respectively; the previously known Ni and Cu analogues have been similarly obtained. Comparison of electrochemical data for these complexes with those of the corresponding metal bis(dithiolene) complexes indicates that substitution of selenium for sulfur does not dramatically alter the electronic structure. Analysis of ESR spectra of the paramagnetic [M(Se2C2(CF3)2)2]- (M = Ni, Pt) anions indicates that the majority (ca. 70%) of the unpaired spin is located on the four selenium atoms. The neutral complex [Pt-(Se2C2(CF3)2)2] exhibits an unusual associational equilibrium in solution that has been studied by UV-vis and 19F NMR spectroscopy. The X-ray crystal structure of [(C6H5)4P] [Pt(Se2C2(CF3)2)2] also is reported; the coordination geometry of Pt is nominally square planar, with interatomic distances reflecting substantial multiple-bond character in the Pt-Se bonds. Crystal data: monoclinic, space group P21/c, with a = 18.015 (3) {\AA}, b = 14.280 (4) {\AA}, c = 14.627 (4) {\AA}, β = 112.30 (2)°, V = 3481.4 (9) {\AA} 3, and Z = 4.",

author = "Heuer, {William B.} and True, {Anne E.} and Swepston, {Paul N.} and Hoffman, {Brian M.}",

year = "1988",

month = apr,

day = "1",

doi = "10.1021/ic00281a033",

language = "English (US)",

volume = "27",

pages = "1474--1482",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "8",

}

Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se₂C₂(CF₃)₂)₂]^z (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C₆H₅)₄P][Pt(Se₂C₂(CF₃)₂)₂]. / Heuer, William B.; True, Anne E.; Swepston, Paul N. et al.
In: Inorganic chemistry, Vol. 27, No. 8, 01.04.1988, p. 1474-1482.

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

TY - JOUR

T1 - Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C6H5)4P][Pt(Se2C2(CF3)2)2]

AU - Heuer, William B.

AU - True, Anne E.

AU - Swepston, Paul N.

AU - Hoffman, Brian M.

PY - 1988/4/1

Y1 - 1988/4/1

N2 - New metal diselenolene complexes with the formula [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) have been prepared by the reaction of bis(trifluoromethyl)diselenete, (CF3)2C2Se2, with (Ph3P)2PtCl2 and (Ph3P)AuCl, respectively; the previously known Ni and Cu analogues have been similarly obtained. Comparison of electrochemical data for these complexes with those of the corresponding metal bis(dithiolene) complexes indicates that substitution of selenium for sulfur does not dramatically alter the electronic structure. Analysis of ESR spectra of the paramagnetic [M(Se2C2(CF3)2)2]- (M = Ni, Pt) anions indicates that the majority (ca. 70%) of the unpaired spin is located on the four selenium atoms. The neutral complex [Pt-(Se2C2(CF3)2)2] exhibits an unusual associational equilibrium in solution that has been studied by UV-vis and 19F NMR spectroscopy. The X-ray crystal structure of [(C6H5)4P] [Pt(Se2C2(CF3)2)2] also is reported; the coordination geometry of Pt is nominally square planar, with interatomic distances reflecting substantial multiple-bond character in the Pt-Se bonds. Crystal data: monoclinic, space group P21/c, with a = 18.015 (3) Å, b = 14.280 (4) Å, c = 14.627 (4) Å, β = 112.30 (2)°, V = 3481.4 (9) Å 3, and Z = 4.

AB - New metal diselenolene complexes with the formula [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) have been prepared by the reaction of bis(trifluoromethyl)diselenete, (CF3)2C2Se2, with (Ph3P)2PtCl2 and (Ph3P)AuCl, respectively; the previously known Ni and Cu analogues have been similarly obtained. Comparison of electrochemical data for these complexes with those of the corresponding metal bis(dithiolene) complexes indicates that substitution of selenium for sulfur does not dramatically alter the electronic structure. Analysis of ESR spectra of the paramagnetic [M(Se2C2(CF3)2)2]- (M = Ni, Pt) anions indicates that the majority (ca. 70%) of the unpaired spin is located on the four selenium atoms. The neutral complex [Pt-(Se2C2(CF3)2)2] exhibits an unusual associational equilibrium in solution that has been studied by UV-vis and 19F NMR spectroscopy. The X-ray crystal structure of [(C6H5)4P] [Pt(Se2C2(CF3)2)2] also is reported; the coordination geometry of Pt is nominally square planar, with interatomic distances reflecting substantial multiple-bond character in the Pt-Se bonds. Crystal data: monoclinic, space group P21/c, with a = 18.015 (3) Å, b = 14.280 (4) Å, c = 14.627 (4) Å, β = 112.30 (2)°, V = 3481.4 (9) Å 3, and Z = 4.

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U2 - 10.1021/ic00281a033

DO - 10.1021/ic00281a033

M3 - Article

AN - SCOPUS:0000896141

SN - 0020-1669

VL - 27

SP - 1474

EP - 1482

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 8

ER -

Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se₂C₂(CF₃)₂)₂]^z (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C₆H₅)₄P][Pt(Se₂C₂(CF₃)₂)₂]

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