Solar Energy Storage Reactions. Determination of the Structure of the Complex Formed by Visible Irradiation of Rh2(bridge)42+ in Aqueous HC1 Solutions

Kent R. Mann; Robert A. Bell; Harry B. Gray

doi:10.1021/ic50200a006

Solar Energy Storage Reactions. Determination of the Structure of the Complex Formed by Visible Irradiation of Rh2(bridge)42+ in Aqueous HC1 Solutions

Kent R. Mann, Robert A. Bell, Harry B. Gray

Chemistry (Twin Cities)

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

56 Scopus citations

Abstract

Visible irradiation of Rh2 (bridge)42+ in concentrated HC1 solutions yields hydrogen gas and a yellow complex, Rh2(bridge)4Cl22+. An X-ray crystal structure analysis of [Rh2(bridge)4Cl2]Cl2-8H20 (bridge=1,3-diisocyanopropane) has been completed (final RF=0.031). The complex crystallizes in the space group [formula omitted]. The structure is composed of Rh2(bridge)4Cl22+ cations having approximate D4h symmetry and a hydrogen-bonded network of CI” anions and water molecules. Each Rh atom is six-coordinate with CI and Rh atoms in axial positions of a Cl(RhC4) Rh unit. The RhRh distance in the binuclear cation is 2.837 (1) υ, and RhCl is 2.447 (1) υ. The relative ease of reductive elimination of X from Rh2(bridge)4X22+ (×=CI, Br) complexes may be explained in part by the drive to reduce CC' and NN' nonbonded-atom repulsions that are caused by the close approach (—2.85 υ) of the Rh(CN)4 planes.

Original language	English (US)
Pages (from-to)	2671-2673
Number of pages	3
Journal	Inorganic Chemistry
Volume	18
Issue number	10
DOIs	https://doi.org/10.1021/ic50200a006
State	Published - Jan 1 1979

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title = "Solar Energy Storage Reactions. Determination of the Structure of the Complex Formed by Visible Irradiation of Rh2(bridge)42+ in Aqueous HC1 Solutions",

abstract = "Visible irradiation of Rh2 (bridge)42+ in concentrated HC1 solutions yields hydrogen gas and a yellow complex, Rh2(bridge)4Cl22+. An X-ray crystal structure analysis of [Rh2(bridge)4Cl2]Cl2-8H20 (bridge=1,3-diisocyanopropane) has been completed (final RF=0.031). The complex crystallizes in the space group [formula omitted]. The structure is composed of Rh2(bridge)4Cl22+ cations having approximate D4h symmetry and a hydrogen-bonded network of CI” anions and water molecules. Each Rh atom is six-coordinate with CI and Rh atoms in axial positions of a Cl(RhC4) Rh unit. The RhRh distance in the binuclear cation is 2.837 (1) υ, and RhCl is 2.447 (1) υ. The relative ease of reductive elimination of X from Rh2(bridge)4X22+ (×=CI, Br) complexes may be explained in part by the drive to reduce CC' and NN' nonbonded-atom repulsions that are caused by the close approach (—2.85 υ) of the Rh(CN)4 planes.",

author = "Mann, {Kent R.} and Bell, {Robert A.} and Gray, {Harry B.}",

year = "1979",

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T1 - Solar Energy Storage Reactions. Determination of the Structure of the Complex Formed by Visible Irradiation of Rh2(bridge)42+ in Aqueous HC1 Solutions

AU - Mann, Kent R.

AU - Bell, Robert A.

AU - Gray, Harry B.

PY - 1979/1/1

Y1 - 1979/1/1

N2 - Visible irradiation of Rh2 (bridge)42+ in concentrated HC1 solutions yields hydrogen gas and a yellow complex, Rh2(bridge)4Cl22+. An X-ray crystal structure analysis of [Rh2(bridge)4Cl2]Cl2-8H20 (bridge=1,3-diisocyanopropane) has been completed (final RF=0.031). The complex crystallizes in the space group [formula omitted]. The structure is composed of Rh2(bridge)4Cl22+ cations having approximate D4h symmetry and a hydrogen-bonded network of CI” anions and water molecules. Each Rh atom is six-coordinate with CI and Rh atoms in axial positions of a Cl(RhC4) Rh unit. The RhRh distance in the binuclear cation is 2.837 (1) υ, and RhCl is 2.447 (1) υ. The relative ease of reductive elimination of X from Rh2(bridge)4X22+ (×=CI, Br) complexes may be explained in part by the drive to reduce CC' and NN' nonbonded-atom repulsions that are caused by the close approach (—2.85 υ) of the Rh(CN)4 planes.

AB - Visible irradiation of Rh2 (bridge)42+ in concentrated HC1 solutions yields hydrogen gas and a yellow complex, Rh2(bridge)4Cl22+. An X-ray crystal structure analysis of [Rh2(bridge)4Cl2]Cl2-8H20 (bridge=1,3-diisocyanopropane) has been completed (final RF=0.031). The complex crystallizes in the space group [formula omitted]. The structure is composed of Rh2(bridge)4Cl22+ cations having approximate D4h symmetry and a hydrogen-bonded network of CI” anions and water molecules. Each Rh atom is six-coordinate with CI and Rh atoms in axial positions of a Cl(RhC4) Rh unit. The RhRh distance in the binuclear cation is 2.837 (1) υ, and RhCl is 2.447 (1) υ. The relative ease of reductive elimination of X from Rh2(bridge)4X22+ (×=CI, Br) complexes may be explained in part by the drive to reduce CC' and NN' nonbonded-atom repulsions that are caused by the close approach (—2.85 υ) of the Rh(CN)4 planes.

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Solar Energy Storage Reactions. Determination of the Structure of the Complex Formed by Visible Irradiation of Rh2(bridge)42+ in Aqueous HC1 Solutions

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