Rhenium polyhydride complexes that contain the tripodal phosphine CH3C(CH2PPh2)3 (triphos)

Michael T. Costello, Phillip E. Fanwick, Mark A. Green, Mark Green

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The compound ReCl3(triphos) (triphos = CH3C(CH2PPh2)3) reacts with NaBH4 in ethanol to afford the pentahydrido complex ReH5(triphos), which when treated with HBF4·Et2O in RCN (R = Me, Et) converts to [ReH(NCR)3(triphos)](BF4)2. The direct reaction of ReH5(triphos) with EPh3 (E = P, As, Sb), dppe (Ph2PCH2CH2PPh2), and arphos (Ph2PCH2CH2AsPh2) produces the trihydrides ReH3(triphos)(EPh3), ReH3(triphos)(η1-dppe), and ReH3(triphos)(η1-arphos), respectively, the latter complex existing as a mixture of linkage isomers ReH3(triphos)(arphos-P) and ReH3(triphos)(arphos-As). A more convenient and higher yield preparation of the compounds ReH3(triphos)L involves the direct reaction of ReCl3(triphos) with NaBH4 and EPh3, dppe, or arphos. The trihydrides can be protonated by HBF4·Et2O to produce [ReH4(triphos)L]BF4, which are in turn readily deprotonated by NEt3. In the absence of ligand L, solutions of ReH5(triphos) evolve H2 and the dark red dinuclear complex Re2H4(triphos)2 is formed cleanly. It is very easily oxidized (E1/2(ox) = -0.55 V vs Ag/AgCl in 0.1 M TBAH-CH2Cl2) to the green monocation [Re2H4(triphos)2]+. Single-crystal X-ray structure determinations have been carried out on the compounds fac-ReCl3(triphos) (1) and [Re2H4(triphos)2]ReO4·5C 6H6 (2). Crystal data for 1 at 20°C: orthorhombic space group Pna21, a = 17.332 (5) Å, b = 12.032 (3) Å, c = 17.542 (4) Å, V = 3658 (3) Å3, and Z = 4. The structure was refined to R = 0.039 (Rw = 0.047) for 1812 data with I > 3σ(I). Crystal data for 2 at -61°C: monoclinic space group P21/n, a = 16.765 (2) Å, b = 23.065 (3) Å, c = 25.109 (4) Å, β = 98.38 (1)°, V = 9605 (4) Å3, and Z = 4. The structure was refined to R = 0.028 (Rw = 0.035) for 9496 data with I > 3.0σ(I). The structure of the cation can be represented as [(triphos)HRe(μ-H)3Re(triphos)]+. Although the terminally bound hydride ligand was not located in this structure determination, its position can be inferred from the angular distortions that are present about one of the Re atoms. The Re-Re distance of 2.5389 (4) Å is typical of a mixed polyhydride-phosphine complex of dirhenium in which there are three or four bridging hydride ligands present.

Original languageEnglish (US)
Pages (from-to)2359-2365
Number of pages7
JournalInorganic Chemistry
Volume31
Issue number12
StatePublished - 1992
Externally publishedYes

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phosphine
Rhenium
rhenium
phosphines
Ligands
Hydrides
ligands
hydrides
Crystals
linkages
Isomers
crystals
Cations
ethyl alcohol
Ethanol
isomers
Single crystals
cations
X rays
Atoms

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Rhenium polyhydride complexes that contain the tripodal phosphine CH3C(CH2PPh2)3 (triphos). / Costello, Michael T.; Fanwick, Phillip E.; Green, Mark A.; Green, Mark.

In: Inorganic Chemistry, Vol. 31, No. 12, 1992, p. 2359-2365.

Research output: Contribution to journalArticle

Costello, MT, Fanwick, PE, Green, MA & Green, M 1992, 'Rhenium polyhydride complexes that contain the tripodal phosphine CH3C(CH2PPh2)3 (triphos)', Inorganic Chemistry, vol. 31, no. 12, pp. 2359-2365.
Costello, Michael T. ; Fanwick, Phillip E. ; Green, Mark A. ; Green, Mark. / Rhenium polyhydride complexes that contain the tripodal phosphine CH3C(CH2PPh2)3 (triphos). In: Inorganic Chemistry. 1992 ; Vol. 31, No. 12. pp. 2359-2365.
@article{98b99c6adb074096ace5d9d9066b4a8f,
title = "Rhenium polyhydride complexes that contain the tripodal phosphine CH3C(CH2PPh2)3 (triphos)",
abstract = "The compound ReCl3(triphos) (triphos = CH3C(CH2PPh2)3) reacts with NaBH4 in ethanol to afford the pentahydrido complex ReH5(triphos), which when treated with HBF4·Et2O in RCN (R = Me, Et) converts to [ReH(NCR)3(triphos)](BF4)2. The direct reaction of ReH5(triphos) with EPh3 (E = P, As, Sb), dppe (Ph2PCH2CH2PPh2), and arphos (Ph2PCH2CH2AsPh2) produces the trihydrides ReH3(triphos)(EPh3), ReH3(triphos)(η1-dppe), and ReH3(triphos)(η1-arphos), respectively, the latter complex existing as a mixture of linkage isomers ReH3(triphos)(arphos-P) and ReH3(triphos)(arphos-As). A more convenient and higher yield preparation of the compounds ReH3(triphos)L involves the direct reaction of ReCl3(triphos) with NaBH4 and EPh3, dppe, or arphos. The trihydrides can be protonated by HBF4·Et2O to produce [ReH4(triphos)L]BF4, which are in turn readily deprotonated by NEt3. In the absence of ligand L, solutions of ReH5(triphos) evolve H2 and the dark red dinuclear complex Re2H4(triphos)2 is formed cleanly. It is very easily oxidized (E1/2(ox) = -0.55 V vs Ag/AgCl in 0.1 M TBAH-CH2Cl2) to the green monocation [Re2H4(triphos)2]+. Single-crystal X-ray structure determinations have been carried out on the compounds fac-ReCl3(triphos) (1) and [Re2H4(triphos)2]ReO4·5C 6H6 (2). Crystal data for 1 at 20°C: orthorhombic space group Pna21, a = 17.332 (5) {\AA}, b = 12.032 (3) {\AA}, c = 17.542 (4) {\AA}, V = 3658 (3) {\AA}3, and Z = 4. The structure was refined to R = 0.039 (Rw = 0.047) for 1812 data with I > 3σ(I). Crystal data for 2 at -61°C: monoclinic space group P21/n, a = 16.765 (2) {\AA}, b = 23.065 (3) {\AA}, c = 25.109 (4) {\AA}, β = 98.38 (1)°, V = 9605 (4) {\AA}3, and Z = 4. The structure was refined to R = 0.028 (Rw = 0.035) for 9496 data with I > 3.0σ(I). The structure of the cation can be represented as [(triphos)HRe(μ-H)3Re(triphos)]+. Although the terminally bound hydride ligand was not located in this structure determination, its position can be inferred from the angular distortions that are present about one of the Re atoms. The Re-Re distance of 2.5389 (4) {\AA} is typical of a mixed polyhydride-phosphine complex of dirhenium in which there are three or four bridging hydride ligands present.",
author = "Costello, {Michael T.} and Fanwick, {Phillip E.} and Green, {Mark A.} and Mark Green",
year = "1992",
language = "English (US)",
volume = "31",
pages = "2359--2365",
journal = "Inorganic Chemistry",
issn = "0020-1669",
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TY - JOUR

T1 - Rhenium polyhydride complexes that contain the tripodal phosphine CH3C(CH2PPh2)3 (triphos)

AU - Costello, Michael T.

AU - Fanwick, Phillip E.

AU - Green, Mark A.

AU - Green, Mark

PY - 1992

Y1 - 1992

N2 - The compound ReCl3(triphos) (triphos = CH3C(CH2PPh2)3) reacts with NaBH4 in ethanol to afford the pentahydrido complex ReH5(triphos), which when treated with HBF4·Et2O in RCN (R = Me, Et) converts to [ReH(NCR)3(triphos)](BF4)2. The direct reaction of ReH5(triphos) with EPh3 (E = P, As, Sb), dppe (Ph2PCH2CH2PPh2), and arphos (Ph2PCH2CH2AsPh2) produces the trihydrides ReH3(triphos)(EPh3), ReH3(triphos)(η1-dppe), and ReH3(triphos)(η1-arphos), respectively, the latter complex existing as a mixture of linkage isomers ReH3(triphos)(arphos-P) and ReH3(triphos)(arphos-As). A more convenient and higher yield preparation of the compounds ReH3(triphos)L involves the direct reaction of ReCl3(triphos) with NaBH4 and EPh3, dppe, or arphos. The trihydrides can be protonated by HBF4·Et2O to produce [ReH4(triphos)L]BF4, which are in turn readily deprotonated by NEt3. In the absence of ligand L, solutions of ReH5(triphos) evolve H2 and the dark red dinuclear complex Re2H4(triphos)2 is formed cleanly. It is very easily oxidized (E1/2(ox) = -0.55 V vs Ag/AgCl in 0.1 M TBAH-CH2Cl2) to the green monocation [Re2H4(triphos)2]+. Single-crystal X-ray structure determinations have been carried out on the compounds fac-ReCl3(triphos) (1) and [Re2H4(triphos)2]ReO4·5C 6H6 (2). Crystal data for 1 at 20°C: orthorhombic space group Pna21, a = 17.332 (5) Å, b = 12.032 (3) Å, c = 17.542 (4) Å, V = 3658 (3) Å3, and Z = 4. The structure was refined to R = 0.039 (Rw = 0.047) for 1812 data with I > 3σ(I). Crystal data for 2 at -61°C: monoclinic space group P21/n, a = 16.765 (2) Å, b = 23.065 (3) Å, c = 25.109 (4) Å, β = 98.38 (1)°, V = 9605 (4) Å3, and Z = 4. The structure was refined to R = 0.028 (Rw = 0.035) for 9496 data with I > 3.0σ(I). The structure of the cation can be represented as [(triphos)HRe(μ-H)3Re(triphos)]+. Although the terminally bound hydride ligand was not located in this structure determination, its position can be inferred from the angular distortions that are present about one of the Re atoms. The Re-Re distance of 2.5389 (4) Å is typical of a mixed polyhydride-phosphine complex of dirhenium in which there are three or four bridging hydride ligands present.

AB - The compound ReCl3(triphos) (triphos = CH3C(CH2PPh2)3) reacts with NaBH4 in ethanol to afford the pentahydrido complex ReH5(triphos), which when treated with HBF4·Et2O in RCN (R = Me, Et) converts to [ReH(NCR)3(triphos)](BF4)2. The direct reaction of ReH5(triphos) with EPh3 (E = P, As, Sb), dppe (Ph2PCH2CH2PPh2), and arphos (Ph2PCH2CH2AsPh2) produces the trihydrides ReH3(triphos)(EPh3), ReH3(triphos)(η1-dppe), and ReH3(triphos)(η1-arphos), respectively, the latter complex existing as a mixture of linkage isomers ReH3(triphos)(arphos-P) and ReH3(triphos)(arphos-As). A more convenient and higher yield preparation of the compounds ReH3(triphos)L involves the direct reaction of ReCl3(triphos) with NaBH4 and EPh3, dppe, or arphos. The trihydrides can be protonated by HBF4·Et2O to produce [ReH4(triphos)L]BF4, which are in turn readily deprotonated by NEt3. In the absence of ligand L, solutions of ReH5(triphos) evolve H2 and the dark red dinuclear complex Re2H4(triphos)2 is formed cleanly. It is very easily oxidized (E1/2(ox) = -0.55 V vs Ag/AgCl in 0.1 M TBAH-CH2Cl2) to the green monocation [Re2H4(triphos)2]+. Single-crystal X-ray structure determinations have been carried out on the compounds fac-ReCl3(triphos) (1) and [Re2H4(triphos)2]ReO4·5C 6H6 (2). Crystal data for 1 at 20°C: orthorhombic space group Pna21, a = 17.332 (5) Å, b = 12.032 (3) Å, c = 17.542 (4) Å, V = 3658 (3) Å3, and Z = 4. The structure was refined to R = 0.039 (Rw = 0.047) for 1812 data with I > 3σ(I). Crystal data for 2 at -61°C: monoclinic space group P21/n, a = 16.765 (2) Å, b = 23.065 (3) Å, c = 25.109 (4) Å, β = 98.38 (1)°, V = 9605 (4) Å3, and Z = 4. The structure was refined to R = 0.028 (Rw = 0.035) for 9496 data with I > 3.0σ(I). The structure of the cation can be represented as [(triphos)HRe(μ-H)3Re(triphos)]+. Although the terminally bound hydride ligand was not located in this structure determination, its position can be inferred from the angular distortions that are present about one of the Re atoms. The Re-Re distance of 2.5389 (4) Å is typical of a mixed polyhydride-phosphine complex of dirhenium in which there are three or four bridging hydride ligands present.

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