Synthesis and reactivity of a very strong reducing agent containing a quadruple bond: Structures of W2(hpp)4 and W2(hpp)4Cl2 · 4CH2Cl2

F. Albert Cotton; Penglin Huang; Carlos A. Murillo; Xiaoping Wang

doi:10.1016/S1387-7003(02)00701-3

Synthesis and reactivity of a very strong reducing agent containing a quadruple bond: Structures of W₂(hpp)₄ and W₂(hpp)₄Cl₂ · 4CH₂Cl₂

F. Albert Cotton, Penglin Huang, Carlos A. Murillo, Xiaoping Wang

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

27 Scopus citations

Abstract

The preparation and structural characterization of the very strong reducing agent W₂(hpp)₄, hpp = the anion of 1,3,4,6,7, 8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, 1, has been accomplished. It has a short distance of 2.1617(4) Å for the quadruply-bonded W₂⁴⁺ unit. Compound 1 is very reactive and gives the triple bonded W₂(hpp)₄Cl₂· 4CH₂Cl₂, 2 · 4CH₂Cl₂, upon crystallization after mere contact with the haloalkane CH₂Cl₂. The change in electronic configuration from the σ²π⁴δ² in 1 to the σ²π⁴ system in 2 increases the W-W distance by ca. 0.09 to 2.2497(8) Å. W₂(hpp)₄ also reduces C₆₀ and 7, 7′, 8, 8′-tetracyanoquinodimethide, TCNQ. The latter is reduced to the TCNQ^2- anion while the W₂⁴⁺ unit is oxidized to the W₂⁶⁺ state.

Original language	English
Pages (from-to)	121-126
Number of pages	6
Journal	Inorganic Chemistry Communications
Volume	6
Issue number	2
DOIs	https://doi.org/10.1016/S1387-7003(02)00701-3
State	Published - Feb 1 2003
Externally published	Yes

Funding

We are grateful to the Robert A. Welch Foundation for financial support.

Funders	Funder number
Welch Foundation

Keywords

Ditungsten
Guanidinate ligands
Metal-metal bonds
Strong reducing agent

Access to Document

10.1016/S1387-7003(02)00701-3

Cite this

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title = "Synthesis and reactivity of a very strong reducing agent containing a quadruple bond: Structures of W2(hpp)4 and W2(hpp)4Cl2 · 4CH2Cl2",

abstract = "The preparation and structural characterization of the very strong reducing agent W2(hpp)4, hpp = the anion of 1,3,4,6,7, 8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, 1, has been accomplished. It has a short distance of 2.1617(4) {\AA} for the quadruply-bonded W24+ unit. Compound 1 is very reactive and gives the triple bonded W2(hpp)4Cl2· 4CH2Cl2, 2 · 4CH2Cl2, upon crystallization after mere contact with the haloalkane CH2Cl2. The change in electronic configuration from the σ2π4δ2 in 1 to the σ2π4 system in 2 increases the W-W distance by ca. 0.09 to 2.2497(8) {\AA}. W2(hpp)4 also reduces C60 and 7, 7′, 8, 8′-tetracyanoquinodimethide, TCNQ. The latter is reduced to the TCNQ2- anion while the W24+ unit is oxidized to the W26+ state.",

keywords = "Ditungsten, Guanidinate ligands, Metal-metal bonds, Strong reducing agent",

author = "Cotton, {F. Albert} and Penglin Huang and Murillo, {Carlos A.} and Xiaoping Wang",

year = "2003",

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language = "English",

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T1 - Synthesis and reactivity of a very strong reducing agent containing a quadruple bond

T2 - Structures of W2(hpp)4 and W2(hpp)4Cl2 · 4CH2Cl2

AU - Cotton, F. Albert

AU - Huang, Penglin

AU - Murillo, Carlos A.

AU - Wang, Xiaoping

PY - 2003/2/1

Y1 - 2003/2/1

N2 - The preparation and structural characterization of the very strong reducing agent W2(hpp)4, hpp = the anion of 1,3,4,6,7, 8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, 1, has been accomplished. It has a short distance of 2.1617(4) Å for the quadruply-bonded W24+ unit. Compound 1 is very reactive and gives the triple bonded W2(hpp)4Cl2· 4CH2Cl2, 2 · 4CH2Cl2, upon crystallization after mere contact with the haloalkane CH2Cl2. The change in electronic configuration from the σ2π4δ2 in 1 to the σ2π4 system in 2 increases the W-W distance by ca. 0.09 to 2.2497(8) Å. W2(hpp)4 also reduces C60 and 7, 7′, 8, 8′-tetracyanoquinodimethide, TCNQ. The latter is reduced to the TCNQ2- anion while the W24+ unit is oxidized to the W26+ state.

AB - The preparation and structural characterization of the very strong reducing agent W2(hpp)4, hpp = the anion of 1,3,4,6,7, 8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, 1, has been accomplished. It has a short distance of 2.1617(4) Å for the quadruply-bonded W24+ unit. Compound 1 is very reactive and gives the triple bonded W2(hpp)4Cl2· 4CH2Cl2, 2 · 4CH2Cl2, upon crystallization after mere contact with the haloalkane CH2Cl2. The change in electronic configuration from the σ2π4δ2 in 1 to the σ2π4 system in 2 increases the W-W distance by ca. 0.09 to 2.2497(8) Å. W2(hpp)4 also reduces C60 and 7, 7′, 8, 8′-tetracyanoquinodimethide, TCNQ. The latter is reduced to the TCNQ2- anion while the W24+ unit is oxidized to the W26+ state.

KW - Ditungsten

KW - Guanidinate ligands

KW - Metal-metal bonds

KW - Strong reducing agent

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