Disulfur and diselenium complexes of rhodium and iridium

A. P. Ginsberg, W. E. Lindsell, C. R. Sprinkle, K. W. West, R. L. Cohen

Research output: Contribution to journalArticle

Abstract

Coordinatively unsaturated low-valent rhodium and iridium complexes cleave S8 and Se8 rings and form complexes with the fragments. With square-planar [M(L-L)2]Cl (M = Rh, Ir; L-L = (C6H5)2PCH2CH2P(C 6H5)2 (dppe), (CH3)2PC-H2CH2P(CH3) 2 (dmpe)) this reaction affords the monomeric electrolytes [M(Y2)(L-L)2]Cl (Y2 = S2, Se2). Oligomeric compounds are obtained from the reactions with IrX(CO)(EPh3)2 and RhX(EPh3)3 (X = Cl, Br; E = P, As); the products are [{Ir(Se2)X(CO)(PPh3)}3], [{Ir(Se2)Cl(CO)(AsPh3}3], [{IrS6Cl(CO)(PPh3)2}n], [{RhS3X(PPh3)4}], [{RhSe3Cl(PPh3)}4], and [{RhY2Cl(AsPh3)}n] (Y2 = S2, Se2). In the compounds [M(Y2)(L-L)2]Cl, disulfur and diselenium are side-on bonded to the metal at equatorial positions of a distorted octahedron. An X-ray structure determination of the diselenium complex [Ir(Se2)(dppe)2]Cl·H2O·0.5C 6H6 shows the cation to be very similar to its dioxygen and disulfur analogues. The Se-Se distance is 2.312 (3) Å, about the same as the bond length in Se8 and 0.16 Å longer than the Se-Se bond in the free Se2 molecule. [M(Y2)(L-L)2]+ complexes have ?(S-S) at 510-550 cm-1 and ?(Se-Se) at 300-310 cm-1. The lowest energy feature of their electronic absorption spectra is a weak (e 40-100 M-1 cm-1) band assigned as an a2p?* ? b1 intraligand transition. 193Ir(1/2+ ? 3/2 +) Mössbauer spectra of [Ir(Y2)(dppe)2]Cl give isomer shifts that decrease along the series Y2 = O2, S2, Se2, in parallel with decreasing Y2 electronegativity. The disulfur or diselenium group in [M(Y2)(L-L)2]+ is readily reduced: mercury and tertiary phosphines strip sulfur or selenium from the complex with formation of HgS or HgSe and R3PS or R3PSe; the rate is very sensitive to the electronic environment of the disulfur or diselenium group and to the basicity of the phosphine. Low-valent group 8 metal complexes undergo oxidative addition across the S-S or Se-Se bond, allowing synthesis of the heterometallic (µ-S)2 dimers [(dppe)2Ir(µ-S)2PtL2]X (L = PPh3, X = Cl; L = PEtPh2, X = PF6) and [(dmpe)2Rh(µ-S)2Pt(PPh3)2]Cl, as well as the asymmetric dimer [(dppe)2Ir(µ-Se)2IrCl(CO)(PEt2Ph) 2]Cl. Oxidative addition together with displacement of [M(L-L)2]+ by excess of the addend complex also occurs, giving homometallic (µ-S)2 or (µ-Se)2 dimers such as [{Ir(µ-Se)Cl(CO)(PEt2Ph)2}2]. Iodine adds across the S-S bond of [Ir(S2)(dppe)2]Cl to form the novel cis-octahedral complex [Ir(SI)2(dppe)2]Cl. © 1982 American Chemical Society.

Original languageEnglish
Pages (from-to)3666-3681
Number of pages16
JournalInorganic Chemistry
Volume21
Issue number10
Publication statusPublished - 1982

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Iridium
Rhodium
Carbon Monoxide
Dimers
phosphine
Phosphines
Electronegativity
Coordination Complexes
Bond length
Alkalinity
Selenium
Mercury
Sulfur
Iodine
Isomers
Electrolytes
Cations
Absorption spectra
Metals
Oxygen

Cite this

Ginsberg, A. P., Lindsell, W. E., Sprinkle, C. R., West, K. W., & Cohen, R. L. (1982). Disulfur and diselenium complexes of rhodium and iridium. Inorganic Chemistry, 21(10), 3666-3681.
Ginsberg, A. P. ; Lindsell, W. E. ; Sprinkle, C. R. ; West, K. W. ; Cohen, R. L. / Disulfur and diselenium complexes of rhodium and iridium. In: Inorganic Chemistry. 1982 ; Vol. 21, No. 10. pp. 3666-3681.
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title = "Disulfur and diselenium complexes of rhodium and iridium",
abstract = "Coordinatively unsaturated low-valent rhodium and iridium complexes cleave S8 and Se8 rings and form complexes with the fragments. With square-planar [M(L-L)2]Cl (M = Rh, Ir; L-L = (C6H5)2PCH2CH2P(C 6H5)2 (dppe), (CH3)2PC-H2CH2P(CH3) 2 (dmpe)) this reaction affords the monomeric electrolytes [M(Y2)(L-L)2]Cl (Y2 = S2, Se2). Oligomeric compounds are obtained from the reactions with IrX(CO)(EPh3)2 and RhX(EPh3)3 (X = Cl, Br; E = P, As); the products are [{Ir(Se2)X(CO)(PPh3)}3], [{Ir(Se2)Cl(CO)(AsPh3}3], [{IrS6Cl(CO)(PPh3)2}n], [{RhS3X(PPh3)4}], [{RhSe3Cl(PPh3)}4], and [{RhY2Cl(AsPh3)}n] (Y2 = S2, Se2). In the compounds [M(Y2)(L-L)2]Cl, disulfur and diselenium are side-on bonded to the metal at equatorial positions of a distorted octahedron. An X-ray structure determination of the diselenium complex [Ir(Se2)(dppe)2]Cl·H2O·0.5C 6H6 shows the cation to be very similar to its dioxygen and disulfur analogues. The Se-Se distance is 2.312 (3) {\AA}, about the same as the bond length in Se8 and 0.16 {\AA} longer than the Se-Se bond in the free Se2 molecule. [M(Y2)(L-L)2]+ complexes have ?(S-S) at 510-550 cm-1 and ?(Se-Se) at 300-310 cm-1. The lowest energy feature of their electronic absorption spectra is a weak (e 40-100 M-1 cm-1) band assigned as an a2p?* ? b1 intraligand transition. 193Ir(1/2+ ? 3/2 +) M{\"o}ssbauer spectra of [Ir(Y2)(dppe)2]Cl give isomer shifts that decrease along the series Y2 = O2, S2, Se2, in parallel with decreasing Y2 electronegativity. The disulfur or diselenium group in [M(Y2)(L-L)2]+ is readily reduced: mercury and tertiary phosphines strip sulfur or selenium from the complex with formation of HgS or HgSe and R3PS or R3PSe; the rate is very sensitive to the electronic environment of the disulfur or diselenium group and to the basicity of the phosphine. Low-valent group 8 metal complexes undergo oxidative addition across the S-S or Se-Se bond, allowing synthesis of the heterometallic (µ-S)2 dimers [(dppe)2Ir(µ-S)2PtL2]X (L = PPh3, X = Cl; L = PEtPh2, X = PF6) and [(dmpe)2Rh(µ-S)2Pt(PPh3)2]Cl, as well as the asymmetric dimer [(dppe)2Ir(µ-Se)2IrCl(CO)(PEt2Ph) 2]Cl. Oxidative addition together with displacement of [M(L-L)2]+ by excess of the addend complex also occurs, giving homometallic (µ-S)2 or (µ-Se)2 dimers such as [{Ir(µ-Se)Cl(CO)(PEt2Ph)2}2]. Iodine adds across the S-S bond of [Ir(S2)(dppe)2]Cl to form the novel cis-octahedral complex [Ir(SI)2(dppe)2]Cl. {\circledC} 1982 American Chemical Society.",
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Ginsberg, AP, Lindsell, WE, Sprinkle, CR, West, KW & Cohen, RL 1982, 'Disulfur and diselenium complexes of rhodium and iridium', Inorganic Chemistry, vol. 21, no. 10, pp. 3666-3681.

Disulfur and diselenium complexes of rhodium and iridium. / Ginsberg, A. P.; Lindsell, W. E.; Sprinkle, C. R.; West, K. W.; Cohen, R. L.

In: Inorganic Chemistry, Vol. 21, No. 10, 1982, p. 3666-3681.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Disulfur and diselenium complexes of rhodium and iridium

AU - Ginsberg, A. P.

AU - Lindsell, W. E.

AU - Sprinkle, C. R.

AU - West, K. W.

AU - Cohen, R. L.

PY - 1982

Y1 - 1982

N2 - Coordinatively unsaturated low-valent rhodium and iridium complexes cleave S8 and Se8 rings and form complexes with the fragments. With square-planar [M(L-L)2]Cl (M = Rh, Ir; L-L = (C6H5)2PCH2CH2P(C 6H5)2 (dppe), (CH3)2PC-H2CH2P(CH3) 2 (dmpe)) this reaction affords the monomeric electrolytes [M(Y2)(L-L)2]Cl (Y2 = S2, Se2). Oligomeric compounds are obtained from the reactions with IrX(CO)(EPh3)2 and RhX(EPh3)3 (X = Cl, Br; E = P, As); the products are [{Ir(Se2)X(CO)(PPh3)}3], [{Ir(Se2)Cl(CO)(AsPh3}3], [{IrS6Cl(CO)(PPh3)2}n], [{RhS3X(PPh3)4}], [{RhSe3Cl(PPh3)}4], and [{RhY2Cl(AsPh3)}n] (Y2 = S2, Se2). In the compounds [M(Y2)(L-L)2]Cl, disulfur and diselenium are side-on bonded to the metal at equatorial positions of a distorted octahedron. An X-ray structure determination of the diselenium complex [Ir(Se2)(dppe)2]Cl·H2O·0.5C 6H6 shows the cation to be very similar to its dioxygen and disulfur analogues. The Se-Se distance is 2.312 (3) Å, about the same as the bond length in Se8 and 0.16 Å longer than the Se-Se bond in the free Se2 molecule. [M(Y2)(L-L)2]+ complexes have ?(S-S) at 510-550 cm-1 and ?(Se-Se) at 300-310 cm-1. The lowest energy feature of their electronic absorption spectra is a weak (e 40-100 M-1 cm-1) band assigned as an a2p?* ? b1 intraligand transition. 193Ir(1/2+ ? 3/2 +) Mössbauer spectra of [Ir(Y2)(dppe)2]Cl give isomer shifts that decrease along the series Y2 = O2, S2, Se2, in parallel with decreasing Y2 electronegativity. The disulfur or diselenium group in [M(Y2)(L-L)2]+ is readily reduced: mercury and tertiary phosphines strip sulfur or selenium from the complex with formation of HgS or HgSe and R3PS or R3PSe; the rate is very sensitive to the electronic environment of the disulfur or diselenium group and to the basicity of the phosphine. Low-valent group 8 metal complexes undergo oxidative addition across the S-S or Se-Se bond, allowing synthesis of the heterometallic (µ-S)2 dimers [(dppe)2Ir(µ-S)2PtL2]X (L = PPh3, X = Cl; L = PEtPh2, X = PF6) and [(dmpe)2Rh(µ-S)2Pt(PPh3)2]Cl, as well as the asymmetric dimer [(dppe)2Ir(µ-Se)2IrCl(CO)(PEt2Ph) 2]Cl. Oxidative addition together with displacement of [M(L-L)2]+ by excess of the addend complex also occurs, giving homometallic (µ-S)2 or (µ-Se)2 dimers such as [{Ir(µ-Se)Cl(CO)(PEt2Ph)2}2]. Iodine adds across the S-S bond of [Ir(S2)(dppe)2]Cl to form the novel cis-octahedral complex [Ir(SI)2(dppe)2]Cl. © 1982 American Chemical Society.

AB - Coordinatively unsaturated low-valent rhodium and iridium complexes cleave S8 and Se8 rings and form complexes with the fragments. With square-planar [M(L-L)2]Cl (M = Rh, Ir; L-L = (C6H5)2PCH2CH2P(C 6H5)2 (dppe), (CH3)2PC-H2CH2P(CH3) 2 (dmpe)) this reaction affords the monomeric electrolytes [M(Y2)(L-L)2]Cl (Y2 = S2, Se2). Oligomeric compounds are obtained from the reactions with IrX(CO)(EPh3)2 and RhX(EPh3)3 (X = Cl, Br; E = P, As); the products are [{Ir(Se2)X(CO)(PPh3)}3], [{Ir(Se2)Cl(CO)(AsPh3}3], [{IrS6Cl(CO)(PPh3)2}n], [{RhS3X(PPh3)4}], [{RhSe3Cl(PPh3)}4], and [{RhY2Cl(AsPh3)}n] (Y2 = S2, Se2). In the compounds [M(Y2)(L-L)2]Cl, disulfur and diselenium are side-on bonded to the metal at equatorial positions of a distorted octahedron. An X-ray structure determination of the diselenium complex [Ir(Se2)(dppe)2]Cl·H2O·0.5C 6H6 shows the cation to be very similar to its dioxygen and disulfur analogues. The Se-Se distance is 2.312 (3) Å, about the same as the bond length in Se8 and 0.16 Å longer than the Se-Se bond in the free Se2 molecule. [M(Y2)(L-L)2]+ complexes have ?(S-S) at 510-550 cm-1 and ?(Se-Se) at 300-310 cm-1. The lowest energy feature of their electronic absorption spectra is a weak (e 40-100 M-1 cm-1) band assigned as an a2p?* ? b1 intraligand transition. 193Ir(1/2+ ? 3/2 +) Mössbauer spectra of [Ir(Y2)(dppe)2]Cl give isomer shifts that decrease along the series Y2 = O2, S2, Se2, in parallel with decreasing Y2 electronegativity. The disulfur or diselenium group in [M(Y2)(L-L)2]+ is readily reduced: mercury and tertiary phosphines strip sulfur or selenium from the complex with formation of HgS or HgSe and R3PS or R3PSe; the rate is very sensitive to the electronic environment of the disulfur or diselenium group and to the basicity of the phosphine. Low-valent group 8 metal complexes undergo oxidative addition across the S-S or Se-Se bond, allowing synthesis of the heterometallic (µ-S)2 dimers [(dppe)2Ir(µ-S)2PtL2]X (L = PPh3, X = Cl; L = PEtPh2, X = PF6) and [(dmpe)2Rh(µ-S)2Pt(PPh3)2]Cl, as well as the asymmetric dimer [(dppe)2Ir(µ-Se)2IrCl(CO)(PEt2Ph) 2]Cl. Oxidative addition together with displacement of [M(L-L)2]+ by excess of the addend complex also occurs, giving homometallic (µ-S)2 or (µ-Se)2 dimers such as [{Ir(µ-Se)Cl(CO)(PEt2Ph)2}2]. Iodine adds across the S-S bond of [Ir(S2)(dppe)2]Cl to form the novel cis-octahedral complex [Ir(SI)2(dppe)2]Cl. © 1982 American Chemical Society.

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Ginsberg AP, Lindsell WE, Sprinkle CR, West KW, Cohen RL. Disulfur and diselenium complexes of rhodium and iridium. Inorganic Chemistry. 1982;21(10):3666-3681.