On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine: Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III)

William A. Howard; Kraig A. Wheeler; Daniela Buccella

doi:10.1016/j.molstruc.2020.128750

On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine: Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III)

William A. Howard, Kraig A. Wheeler, Daniela Buccella

Chemistry

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

Abstract

The aim of this work is to identify the products obtained from the chemical reaction between rhodium(III) bromide dihydrate and diphenylphosphine. If three to four equivalents of diphenylphosphine are used, a mixture of colorless trans-[Rh(H) (Br){PH(C₆H₅)₂}₄]Br (product A) and orange trans-[RhBr₂{PH(C₆H₅)₂}₄]⁺ trans-[RhBr₄{PH(C₆H₅)₂}₂]^- (product B) is formed, and these products are easily separated by filtration. Both A and B have been structurally characterized by single-crystal X-ray diffraction. If B is treated with excess diphenylphosphine, or if RhBr₃ · 2H₂O is treated with five or six equivalents of diphenylphosphine, then only A is formed. In CD₃OD solution, H/D exchange occurs in A, leading to the penta-substituted isotopomer trans-[Rh(D) (Br){PD(C₆H₅)₂}₄]Br. Finally, a suspension of B in acetone-d₆ at room temperature led to the formation of red crystals of mer-[RhBr₃{PH(C₆H₅)₂}₃] (product C) after several days. C was also structurally characterized by single-crystal X-ray diffraction.

Original language	English (US)
Article number	128750
Journal	Journal of Molecular Structure
Volume	1220
DOIs	https://doi.org/10.1016/j.molstruc.2020.128750
State	Published - Nov 15 2020

Keywords

Bromide
Diphenylphosphine
Hydride
Rhodium
X-ray structures

ASJC Scopus subject areas

Analytical Chemistry
Spectroscopy
Organic Chemistry
Inorganic Chemistry

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Howard, W. A., Wheeler, K. A., & Buccella, D. (2020). On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine: Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III). Journal of Molecular Structure, 1220, Article 128750. https://doi.org/10.1016/j.molstruc.2020.128750

On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine: Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III). / Howard, William A.; Wheeler, Kraig A.; Buccella, Daniela.
In: Journal of Molecular Structure, Vol. 1220, 128750, 15.11.2020.

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

Howard, WA, Wheeler, KA & Buccella, D 2020, 'On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine: Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III)', Journal of Molecular Structure, vol. 1220, 128750. https://doi.org/10.1016/j.molstruc.2020.128750

Howard WA, Wheeler KA, Buccella D. On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine: Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III). Journal of Molecular Structure. 2020 Nov 15;1220:128750. doi: 10.1016/j.molstruc.2020.128750

Howard, William A. ; Wheeler, Kraig A. ; Buccella, Daniela. / On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine : Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III). In: Journal of Molecular Structure. 2020 ; Vol. 1220.

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title = "On the reaction between rhodium(III) bromide dihydrate and diphenylphosphine: Crystal and molecular structures of Trans-Bromotetrakis(diphenylphosphine)hydridorhodium(III) bromide, Trans-Dibromotetrakis(diphenylphosphine)rhodium(III) Trans-Tetrabromobis(diphenylphosphine)rhodate(III), and Mer-Tribromotris(diphenylphosphine)rhodium(III)",

abstract = "The aim of this work is to identify the products obtained from the chemical reaction between rhodium(III) bromide dihydrate and diphenylphosphine. If three to four equivalents of diphenylphosphine are used, a mixture of colorless trans-[Rh(H) (Br){PH(C6H5)2}4]Br (product A) and orange trans-[RhBr2{PH(C6H5)2}4]+ trans-[RhBr4{PH(C6H5)2}2]- (product B) is formed, and these products are easily separated by filtration. Both A and B have been structurally characterized by single-crystal X-ray diffraction. If B is treated with excess diphenylphosphine, or if RhBr3 · 2H2O is treated with five or six equivalents of diphenylphosphine, then only A is formed. In CD3OD solution, H/D exchange occurs in A, leading to the penta-substituted isotopomer trans-[Rh(D) (Br){PD(C6H5)2}4]Br. Finally, a suspension of B in acetone-d6 at room temperature led to the formation of red crystals of mer-[RhBr3{PH(C6H5)2}3] (product C) after several days. C was also structurally characterized by single-crystal X-ray diffraction.",

keywords = "Bromide, Diphenylphosphine, Hydride, Rhodium, X-ray structures",

author = "Howard, {William A.} and Wheeler, {Kraig A.} and Daniela Buccella",

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AU - Howard, William A.

AU - Wheeler, Kraig A.

AU - Buccella, Daniela

PY - 2020/11/15

Y1 - 2020/11/15

N2 - The aim of this work is to identify the products obtained from the chemical reaction between rhodium(III) bromide dihydrate and diphenylphosphine. If three to four equivalents of diphenylphosphine are used, a mixture of colorless trans-[Rh(H) (Br){PH(C6H5)2}4]Br (product A) and orange trans-[RhBr2{PH(C6H5)2}4]+ trans-[RhBr4{PH(C6H5)2}2]- (product B) is formed, and these products are easily separated by filtration. Both A and B have been structurally characterized by single-crystal X-ray diffraction. If B is treated with excess diphenylphosphine, or if RhBr3 · 2H2O is treated with five or six equivalents of diphenylphosphine, then only A is formed. In CD3OD solution, H/D exchange occurs in A, leading to the penta-substituted isotopomer trans-[Rh(D) (Br){PD(C6H5)2}4]Br. Finally, a suspension of B in acetone-d6 at room temperature led to the formation of red crystals of mer-[RhBr3{PH(C6H5)2}3] (product C) after several days. C was also structurally characterized by single-crystal X-ray diffraction.

AB - The aim of this work is to identify the products obtained from the chemical reaction between rhodium(III) bromide dihydrate and diphenylphosphine. If three to four equivalents of diphenylphosphine are used, a mixture of colorless trans-[Rh(H) (Br){PH(C6H5)2}4]Br (product A) and orange trans-[RhBr2{PH(C6H5)2}4]+ trans-[RhBr4{PH(C6H5)2}2]- (product B) is formed, and these products are easily separated by filtration. Both A and B have been structurally characterized by single-crystal X-ray diffraction. If B is treated with excess diphenylphosphine, or if RhBr3 · 2H2O is treated with five or six equivalents of diphenylphosphine, then only A is formed. In CD3OD solution, H/D exchange occurs in A, leading to the penta-substituted isotopomer trans-[Rh(D) (Br){PD(C6H5)2}4]Br. Finally, a suspension of B in acetone-d6 at room temperature led to the formation of red crystals of mer-[RhBr3{PH(C6H5)2}3] (product C) after several days. C was also structurally characterized by single-crystal X-ray diffraction.

KW - Bromide

KW - Diphenylphosphine

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