Synthesis and Chemistry of New Nickel, Palladium, and Platinum Complexes of 1,2-Ethanedithiol, 1,3-Propanedithiol, 1,4-Butanedithiol, 1,4,8-Trithianonane, and 1,4,8,11-Tetrathiaundecane

Thomas B. Rauchfuss; J. Shing Shu; D. Max Roundhill

doi:10.1021/ic50163a017

Synthesis and Chemistry of New Nickel, Palladium, and Platinum Complexes of 1,2-Ethanedithiol, 1,3-Propanedithiol, 1,4-Butanedithiol, 1,4,8-Trithianonane, and 1,4,8,11-Tetrathiaundecane

Thomas B. Rauchfuss, J. Shing Shu, D. Max Roundhill

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Abstract

Monomers of general formulas M(SPh)₂L₂ (M = Ni, Pd, Pt, L = PMe₂Ph, DPPE, c-HxNC; M = Pd, Pt, L = DIARS) and M(SCH₂CH₂S)L₂ (M = Ni, Pd, Pt, L = PMe₂Ph; M = Ni, L = DPPE; M = Pd, L = DIARS) have been prepared by cleavage of the polymers [M(SPh)₂]_n and [M(SCH₂CH₂S)]_n with the appropriate ligand. Anomalous ¹H NMR spectra are observed for complexes M(SCH₂CH₂S)(PMe₂Ph)₂. Complexes Pt[S(CH₂)₃S]L₂ (L = PPh₃, PMePh₂) and Pt[S(CH₂)₃S](L-L) (L-L = DPPE, v-DPPE), having six-membered rings, and Pt[S(CH₂)₄S](DPPE) having a seven-membered ring, have been prepared. The compound HS(CH₂)₂S(CH₂)₃SMe and its coupled product with 1,3-dibromopropane, MeS(CH₂)₃S(CH₂)₂S(CH ₂)₃S(CH₂)₂S(CH₂) ₃SMe, have been isolated. The former reacts with Pt(PPh₃)₃ to give the compound PtH [S(CH₂)₂S(CH₂)₃SMe] PPh₃, in which the terminal thioether group is uncoordinated. The trimeric oligomer [Ni₃[S(CH₂)₂S(CH₂) ₃S(CH₂)₂S]₂](BF₄) ₂ has been synthesized. The complex shows intense absorptions at 498 nm (ε 3700), 424 nm (ε 8500), and 293 nm (ε 23 200). In acetonitrile solution two polarographic waves are observed at -300 and -700 mV.

Original language	English (US)
Pages (from-to)	2096-2101
Number of pages	6
Journal	Inorganic Chemistry
Volume	15
Issue number	9
DOIs	https://doi.org/10.1021/ic50163a017
State	Published - Sep 1 1976
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Synthesis and Chemistry of New Nickel, Palladium, and Platinum Complexes of 1,2-Ethanedithiol, 1,3-Propanedithiol, 1,4-Butanedithiol, 1,4,8-Trithianonane, and 1,4,8,11-Tetrathiaundecane. / Rauchfuss, Thomas B.; Shu, J. Shing; Roundhill, D. Max.
In: Inorganic Chemistry, Vol. 15, No. 9, 01.09.1976, p. 2096-2101.

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

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title = "Synthesis and Chemistry of New Nickel, Palladium, and Platinum Complexes of 1,2-Ethanedithiol, 1,3-Propanedithiol, 1,4-Butanedithiol, 1,4,8-Trithianonane, and 1,4,8,11-Tetrathiaundecane",

abstract = "Monomers of general formulas M(SPh)2L2 (M = Ni, Pd, Pt, L = PMe2Ph, DPPE, c-HxNC; M = Pd, Pt, L = DIARS) and M(SCH2CH2S)L2 (M = Ni, Pd, Pt, L = PMe2Ph; M = Ni, L = DPPE; M = Pd, L = DIARS) have been prepared by cleavage of the polymers [M(SPh)2]n and [M(SCH2CH2S)]n with the appropriate ligand. Anomalous 1H NMR spectra are observed for complexes M(SCH2CH2S)(PMe2Ph)2. Complexes Pt[S(CH2)3S]L2 (L = PPh3, PMePh2) and Pt[S(CH2)3S](L-L) (L-L = DPPE, v-DPPE), having six-membered rings, and Pt[S(CH2)4S](DPPE) having a seven-membered ring, have been prepared. The compound HS(CH2)2S(CH2)3SMe and its coupled product with 1,3-dibromopropane, MeS(CH2)3S(CH2)2S(CH 2)3S(CH2)2S(CH2) 3SMe, have been isolated. The former reacts with Pt(PPh3)3 to give the compound PtH [S(CH2)2S(CH2)3SMe] PPh3, in which the terminal thioether group is uncoordinated. The trimeric oligomer [Ni3[S(CH2)2S(CH2) 3S(CH2)2S]2](BF4) 2 has been synthesized. The complex shows intense absorptions at 498 nm (ε 3700), 424 nm (ε 8500), and 293 nm (ε 23 200). In acetonitrile solution two polarographic waves are observed at -300 and -700 mV.",

author = "Rauchfuss, {Thomas B.} and Shu, {J. Shing} and Roundhill, {D. Max}",

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AU - Rauchfuss, Thomas B.

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AU - Roundhill, D. Max

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N2 - Monomers of general formulas M(SPh)2L2 (M = Ni, Pd, Pt, L = PMe2Ph, DPPE, c-HxNC; M = Pd, Pt, L = DIARS) and M(SCH2CH2S)L2 (M = Ni, Pd, Pt, L = PMe2Ph; M = Ni, L = DPPE; M = Pd, L = DIARS) have been prepared by cleavage of the polymers [M(SPh)2]n and [M(SCH2CH2S)]n with the appropriate ligand. Anomalous 1H NMR spectra are observed for complexes M(SCH2CH2S)(PMe2Ph)2. Complexes Pt[S(CH2)3S]L2 (L = PPh3, PMePh2) and Pt[S(CH2)3S](L-L) (L-L = DPPE, v-DPPE), having six-membered rings, and Pt[S(CH2)4S](DPPE) having a seven-membered ring, have been prepared. The compound HS(CH2)2S(CH2)3SMe and its coupled product with 1,3-dibromopropane, MeS(CH2)3S(CH2)2S(CH 2)3S(CH2)2S(CH2) 3SMe, have been isolated. The former reacts with Pt(PPh3)3 to give the compound PtH [S(CH2)2S(CH2)3SMe] PPh3, in which the terminal thioether group is uncoordinated. The trimeric oligomer [Ni3[S(CH2)2S(CH2) 3S(CH2)2S]2](BF4) 2 has been synthesized. The complex shows intense absorptions at 498 nm (ε 3700), 424 nm (ε 8500), and 293 nm (ε 23 200). In acetonitrile solution two polarographic waves are observed at -300 and -700 mV.

AB - Monomers of general formulas M(SPh)2L2 (M = Ni, Pd, Pt, L = PMe2Ph, DPPE, c-HxNC; M = Pd, Pt, L = DIARS) and M(SCH2CH2S)L2 (M = Ni, Pd, Pt, L = PMe2Ph; M = Ni, L = DPPE; M = Pd, L = DIARS) have been prepared by cleavage of the polymers [M(SPh)2]n and [M(SCH2CH2S)]n with the appropriate ligand. Anomalous 1H NMR spectra are observed for complexes M(SCH2CH2S)(PMe2Ph)2. Complexes Pt[S(CH2)3S]L2 (L = PPh3, PMePh2) and Pt[S(CH2)3S](L-L) (L-L = DPPE, v-DPPE), having six-membered rings, and Pt[S(CH2)4S](DPPE) having a seven-membered ring, have been prepared. The compound HS(CH2)2S(CH2)3SMe and its coupled product with 1,3-dibromopropane, MeS(CH2)3S(CH2)2S(CH 2)3S(CH2)2S(CH2) 3SMe, have been isolated. The former reacts with Pt(PPh3)3 to give the compound PtH [S(CH2)2S(CH2)3SMe] PPh3, in which the terminal thioether group is uncoordinated. The trimeric oligomer [Ni3[S(CH2)2S(CH2) 3S(CH2)2S]2](BF4) 2 has been synthesized. The complex shows intense absorptions at 498 nm (ε 3700), 424 nm (ε 8500), and 293 nm (ε 23 200). In acetonitrile solution two polarographic waves are observed at -300 and -700 mV.

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Synthesis and Chemistry of New Nickel, Palladium, and Platinum Complexes of 1,2-Ethanedithiol, 1,3-Propanedithiol, 1,4-Butanedithiol, 1,4,8-Trithianonane, and 1,4,8,11-Tetrathiaundecane

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